JP6649259B2 - Composition of resin-linear organosiloxane block copolymer - Google Patents

Description

Cross-reference of related applications

  This application claims the benefit of US Provisional Patent Application No. 61 / 879,447, filed September 18, 2013, as if fully set forth herein. Incorporated by reference.

  Many electronic devices use encapsulant coatings to protect electronic components from environmental factors. These protective coatings must be tough, durable, long lasting, easy to apply, and cure in a relatively short period of time without unwanted by-products. However, many of the currently available coatings lack toughness, are not durable, do not last long, are not easy to apply, and in certain applications do not cure quickly enough, and in some cases, This produces unwanted by-products. Therefore, there is a continuing need in many new technical fields to identify protective and / or functional coatings.

Embodiment 1 is an organosiloxane block copolymer,
Disiloxy unit of the formula _^[R 1 _{2 SiO 2/2]} of 40 to 90 mole percent,
Torishirokishi units of the formula ^[R _{2 SiO 3/2]} of 10 to 60 mole percent,
From 0.5 to 35 mole percent silanol groups [@SiOH];
Where:
Each R ¹ is independently a C ₁ -C ₃₀ hydrocarbyl or a C ₁ -C ₃₀ hydrocarbyl group containing at least one aliphatic unsaturated bond;
Each R ² is independently a C ₁ -C ₃₀ hydrocarbyl or a C ₁ -C ₃₀ hydrocarbyl group containing at least one aliphatic unsaturated bond;
here,
The disiloxy unit _^[R 1 _{2 SiO 2/2]} are arranged in linear blocks having an average per linear block 50-300 amino disiloxy unit _^[R 1 _{2 SiO 2/2]} ,
The trisiloxy units [R ² SiO _3/2 ] are arranged in a non-linear block having a molecular weight of at least 500 g / mol;
At least 30% of the non-linear blocks are cross-linked to each other;
Each linear block is linked to at least one non-linear block via a -Si-O-Si- bond;
The organosiloxane block copolymer has a weight average molecular weight of at least 20,000 g / mol, and
Said organosiloxane block copolymer comprises C ₁ -C ₃₀ hydrocarbyl group containing at least one aliphatic unsaturation of from about 0.5 to about 5 mole%, relating to organosiloxane block copolymer.

  Embodiment 2 relates to the organosiloxane block copolymer of Embodiment 1, wherein the organosiloxane block copolymer has a weight average molecular weight of about 40,000 g / mol to about 250,000 g / mol.

  Embodiment 3 relates to the organosiloxane block copolymer of Embodiments 1-2, wherein the organosiloxane block copolymer comprises 1-35 mole percent of silanol groups [@SiOH].

Embodiment 4 is an organosiloxane block copolymer comprises Torishirokishi units of the formula ^[R _{2 SiO 3/2]} from 30 to 60 mole percent, about organosiloxane block copolymer embodiment 1-3.

Embodiment 5
A) A resin linear organosiloxane block copolymer,
Disiloxy unit of the formula _^[R 1 _{2 SiO 2/2]} of 40 to 90 mole percent,
Torishirokishi units of the formula ^[R _{2 SiO 3/2]} of 10 to 60 mole percent,
From 0.5 to 35 mole percent silanol groups [@SiOH];
Where:
Each R ¹ is independently C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation;
Each R ² is independently a C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation;
here,
The disiloxy unit _^[R 1 _{2 SiO 2/2]} are arranged in linear blocks having an average per linear block 50-300 amino disiloxy unit _^[R 1 _{2 SiO 2/2]} ,
The trisiloxy units [R ² SiO _3/2 ] are arranged in non-linear blocks having a molecular weight of at least 500 g / mol, at least 30% of the non-linear blocks being cross-linked to one another,
Each linear block is linked to at least one non-linear block, and
The organosiloxane block copolymer comprises a resin-linear organosiloxane block copolymer having a weight average molecular weight of at least 20,000 g / mol;
B) a compound of formula ^R 1 ^R _{2 2} SiX,
Wherein each R ¹ is independently a C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation or a C ₁ -C ₃₀ hydrocarbyl group containing at least one aliphatic unsaturated bond;
Each R ² is independently a C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation or a C ₁ -C ₃₀ hydrocarbyl group containing at least one aliphatic unsaturated bond;
X ^is a -OR 4, F, Cl, Br , I, -OC (O) R 4, -N (R 4) 2, or a hydrolyzable group selected from -ON = ^CR _{4 2,} Wherein R ⁴ is hydrogen or an optionally substituted C ₁ -C ₆ alkyl group.

  Embodiment 6 relates to the composition of Embodiment 5, wherein the resinous linear organosiloxane block copolymer has a weight average molecular weight of about 40,000 g / mol to about 250,000 g / mol.

  Embodiment 7 relates to the organosiloxane block copolymers of Embodiments 5-6, wherein the organosiloxane block copolymer comprises 1-35 mole percent of silanol groups [@SiOH].

Embodiment 8, the organosiloxane block copolymer comprises Torishirokishi units of the formula ^[R _{2 SiO 3/2]} from 30 to 60 mole percent, about organosiloxane block copolymer embodiment 5-7.

Embodiment 9
A) Formula:
There linear organosiloxanes having ^{_{R 1 3-p (E)}} p SiO (R 1 2 SiO 2/2) n Si (E) p R 1 3-p,
Wherein each R ¹ is independently C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation;
n is 50 to 300,
E ^is a -OR 4, F, Cl, Br , I, -OC (O) R 4, -N (R 4) 2, or a hydrolyzable group selected from -ON = ^CR _{4 2,} Wherein R ⁴ is hydrogen or a C ₁ -C ₆ alkyl group;
Each p is independently 1, 2, or 3, a linear organosiloxane;
B) Unit formula:
^{_{[R 1 2 R 2 SiO 1/2}} ] a [R 1 R 2 SiO 2/2] b [R 1 SiO 3/2] c [R 2 SiO 3/2] d [SiO 4/2] e, the An organosiloxane resin comprising:
Where:
Each R ¹ is independently a C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation or a C ₁ -C ₃₀ hydrocarbyl group containing at least one aliphatic unsaturated bond;
Each R ² is independently a C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation or a C ₁ -C ₃₀ hydrocarbyl group containing at least one aliphatic unsaturated bond;
The organosiloxane resin contains 0 to 35 mol% of a silanol group [@SiOH];
Subscripts a, b, c, d, and e represent the mole fraction of each siloxy unit present in the organosiloxane resin, and the range is
a is from about 0 to about 0.6;
b is from about 0 to about 0.6;
c is from about 0 to about 1,
d is about 0 to about 1,
e is from about 0 to about 0.6;
However, it relates to a composition containing a reaction product with an organosiloxane resin, wherein b + c + d + e> 0 and a + b + c + d + e ≦ 1.

Embodiment 10
A) Formula:
There linear organosiloxanes having ^{_{R 1 3-p (E)}} p SiO (R 1 2 SiO 2/2) n Si (E) p R 1 3-p,
Wherein each R ¹ is independently C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation;
n is 50 to 300,
E ^is a -OR 4, F, Cl, Br , I, -OC (O) R 4, -N (R 4) 2, or a hydrolyzable group selected from -ON = ^CR _{4 2,} Wherein R ⁴ is hydrogen or a C ₁ -C ₆ alkyl group;
Each p is independently 1, 2, or 3, a linear organosiloxane;
B) Unit formula:
Containing ^{_{[R 1 2 R 2 SiO 1/2}} ] a [R 1 R 2 SiO 2/2] b [R 1 SiO 3/2] c [R 2 SiO 3/2] d [SiO 4/2] e An organosiloxane resin,
Where:
Each R ¹ is independently C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation;
Each R ² is independently a C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation;
The organosiloxane resin contains 0 to 35 mol% of a silanol group [@SiOH];
Subscripts a, b, c, d, and e represent the mole fraction of each siloxy unit present in the organosiloxane resin, and the range is
a is from about 0 to about 0.6;
b is from about 0 to about 0.6;
c is from about 0 to about 1,
d is about 0 to about 1,
e is from about 0 to about 0.6;
Where b + c + d + e> 0 and a + b + c + d + e ≦ 1;
C) a compound of the formula R ¹ _q SiX _4-q ,
Wherein each R ¹ is independently a C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation or a C ₁ -C ₃₀ hydrocarbyl group containing at least one aliphatic unsaturated bond;
q is 0, 1, or 2,
Each X is ^{independently,} -OR 4, F, Cl, Br, I, -OC (O) R 4, -N (R 4) 2, or -ON = hydrolyzable selected from ^CR _{4 2} Wherein R ⁴ is hydrogen or an optionally substituted C ₁ -C ₆ alkyl group.

  Embodiment 11 relates to the composition of embodiment 10, wherein the product of the step of contacting A) and B) is contacted with C).

Embodiment 12 is the reaction product of the above is contacted with a compound of the formula ^R ₅ q _{SiX 4-q,} wherein each ^{R 5} is independently _C 1 -C ₈ hydrocarbyl or _C 1 -C ₈ halogen substituted hydrocarbyl, each X is independently ^selected -OR 4, F, Cl, Br , I, -OC (O) R 4, -N (R 4) 2, or from -ON = ^CR _{4 2} Embodiment 5. A composition according to embodiments 5-11, wherein the composition is a hydrolysable group, wherein R ⁴ is hydrogen or an optionally substituted C ₁ -C ₆ alkyl group.

Embodiment 13 provides that the reaction product is an organosiloxane block copolymer, wherein the organosiloxane block copolymer has from about 0.5 to about 5 mol% of a C ₁ -C ₃₀ containing at least one aliphatic unsaturated bond. Embodiment 5. The composition of embodiments 5 to 11 comprising a hydrocarbyl group.

  Embodiment 14 relates to the composition of embodiment 9 or 10, wherein E is acetoxy and p is 1.

Embodiment 15 uses the unit formula:
^{_{[R 1 2 R 2 SiO 1/2}} ] a [R 1 R 2 SiO 2/2] b [R 1 SiO 3/2] c [R 2 SiO 3/2] d have a _{[SiO 4/2] e} And
A compound containing 0 to 35 mol% of silanol groups [≡SiOH],
Where:
Each R ¹ is independently H or C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation;
Each R ² is independently H or C ₁ -C ₃₀ hydrocarbyl free of aliphatic unsaturation;
The subscripts a, b, c, d, and e represent the mole fraction of each siloxy unit present, and the range is:
a is from about 0 to about 0.6;
b is from about 0 to about 0.6;
c is from about 0 to about 1,
d is about 0 to about 1,
e is from about 0 to about 0.6;
However,
b + c + d + e> 0 and a + b + c + d + e ≦ 1;
Embodiment 5. The composition of embodiments 5-14, further comprising a compound wherein at least 1 mol% of R ¹ and / or R ² is H.

  Embodiment 16 relates to the compositions of Embodiments 5 through 15, further comprising a hydrosilylation catalyst.

  Embodiment 17 relates to the compositions of Embodiments 5-16, further comprising a free resin that is not part of the block copolymer.

  Embodiment 18 relates to the compositions of Embodiments 5 through 10, wherein the composition is curable.

  Embodiment 19 relates to the curable composition of Embodiment 18, wherein the curable composition has a cure rate of about 1 to about 20 Pa / min Pa / min at a heating rate of 5 ° C./min.

  Embodiment 20 relates to the curable composition of Embodiment 18, wherein the curable composition is curable by at least two types of curing mechanisms.

  Embodiment 21 relates to the curable composition of Embodiment 20, wherein the at least two curing mechanisms include a hydrosilylation cure and a condensation cure.

  Embodiment 22 relates to the compositions of embodiments 5-10, wherein the composition is a solid.

  Embodiment 23 relates to the composition of Embodiment 22, further comprising a free resin that is not part of the block copolymer.

  Embodiment 24 relates to the composition of embodiment 22, wherein the composition is a solid film composition.

  Embodiment 25 relates to the composition of Embodiment 24, wherein the solid film composition has a light transmittance of at least 95% at a film thickness of 0.5 mm or more.

  Embodiment 26 relates to the cured product of the composition of Embodiments 5-10.

  Embodiment 27 relates to the cured product of Embodiment 26, wherein the product is cured in the absence of a condensation catalyst.

  Embodiment 28 relates to the cured product of embodiment 26, wherein the product is cured in the presence of a phosphor or filler.

  Embodiment 29 relates to the cured product of Embodiment 26, wherein the ratio of the Young's modulus of the cured product after aging at 225 ° C. for 50 hours to the Young's modulus before aging is less than 3.

  Embodiment 30 relates to the cured product of embodiment 26, wherein the cured product generates less than 200 ppm of benzene after 30 minutes at 180 ° C.

Embodiment 31 relates to the cured product of embodiment 26, wherein the CIE b ^* value after aging at 235 ° C. for 72 hours is about 6 or less.

  The present disclosure provides certain “linear resin” organosiloxane block copolymers and methods for preparing curable and solid compositions that include the “linear resin” organosiloxane block copolymer. Although the "resin-linear" organosiloxane block copolymers contain certain, relatively small amounts (in mole percent) of unsaturated groups, a "double cure" mechanism is also envisioned, but at least hydrosilylation Can be cured. In embodiments involving a resinous linear organosiloxane block copolymer with a dual cure mechanism, hydrosilylation can be one cure mechanism. However, in addition to having a specific amount (mol%) of unsaturated groups, the resinous linear organosiloxane block copolymers may have, for example, a condensation cure mechanism, a Diels-Alder cure, an azide-alkyne cycloaddition cure, a radical cure, a UV cure. Or other reactive functional groups (e.g., silanols) that can provide at least one second cure mechanism such as radical acrylate cure, UV epoxy cure, Michael addition, and all reactions classified as "click chemistry". Epoxide groups, cyanate ester groups, azidoalkyne groups, etc.).

It is surprising that hydrosilylated curable resin-linear organosiloxane block copolymers having a relatively small amount of unsaturated groups have significantly faster cure rates compared to their condensation-curable counterparts. And unexpectedly found. Faster cure rates have become a means of encapsulating and curing electronic devices such as light emitting diodes (LEDs) with high throughput, thereby reducing the overall cost of the process and facilitating widespread use of solid state light sources. LED chip devices also generally contain tall structures, such as chips and diodes, which are particularly difficult to encapsulate by, for example, a lamination process. An adjustable fast curing system can provide the level of control needed to succeed in such situations. In addition to having a fast cure rate, hydrosilylation-curable organosiloxane block copolymers exhibit, inter alia, low tack and high storage stability resulting from a relatively high resin glass transition temperature (T _g ). Other benefits associated with the "linear resin" organosiloxane block copolymers described herein, as well as curable solid compositions comprising "linear resin" organosiloxane block copolymers include, but are not limited to, , Good dissipation or stress relaxation behavior (which aids the stress dissipation of the LED device), the ability to accommodate the phosphor particles without adversely affecting the cure rate.
Organosiloxane block copolymer

In some embodiments, the “resin linear” organosiloxane block copolymer is
Disiloxy unit of the formula _^[R 1 _{2 SiO 2/2]} of 40 to 90 mole percent,
Torishirokishi units of the formula ^[R _{2 SiO 3/2]} of 10 to 60 mole percent,
From 0.5 to 35 mole percent silanol groups [@SiOH];
Where:
Each R ¹ is independently a C ₁ -C ₃₀ hydrocarbyl or a C ₁ -C ₃₀ hydrocarbyl group containing at least one aliphatic unsaturated bond;
Each R ² is independently an organosiloxane block copolymer, which is a C ₁ -C ₃₀ hydrocarbyl or a C ₁ -C ₃₀ hydrocarbyl group containing at least one aliphatic unsaturated bond,
here,
The disiloxy unit ^{_{[R 1 2 SiO 2/2] (}} D) is, in the linear block having an average per linear block 10-400 amino disiloxy unit _^[R 1 _{2 SiO 2/2]} Placed in
The trisiloxy units [R ² SiO _3/2 ] (T) are arranged in a non-linear block having a molecular weight of at least 500 g / mol;
At least 30% of the non-linear blocks are cross-linked to each other;
Each linear block is linked to at least one non-linear block via a -Si-O-Si- bond;
The organosiloxane block copolymer has a weight average molecular weight of at least 20,000 g / mol, and
It said organosiloxane block copolymer comprises C ₁ -C ₃₀ hydrocarbyl group containing at least one aliphatic unsaturation of from about 0.5 to about 5 mole%, an organosiloxane block copolymer.

As used herein, "organosiloxane block copolymer" or "resin-linear organosiloxane block copolymer" refers to a "linear" D siloxy unit in combination with a "resin" T siloxy unit. Refers to organopolysiloxane. In some embodiments, the organosiloxane copolymer is a "block" copolymer, as opposed to a "random" copolymer. Embodiments of the present disclosure "resin - linear organosiloxane block copolymer" itself refers to organopolysiloxane containing D and T siloxy units, where D units (i.e., [R 1 ² _SiO ² _{/ 2} ] units) are predominantly linked to one another and, in some embodiments, average 10-400 D units (eg, average about 10-about 350 D units, about 10-about 300 D units, about 10-about 200 D units) About 10 to about 100 D units, about 50 to about 400 D units, about 100 to about 400 D units, about 150 to about 400 D units, about 200 to about 400 D units, about 300 to about 400 D units, about 50 to about 300 D units, About 100 to about 300 D units, about 150 to about 300 D units, about 200 to about 300 D units, about 100 to about 150 D units, about 115 to about 125 D units The polymer chains form having about 90 to about 170D units, or from about 110 to about 140D units), this is referred to as "linear block" herein.

The T units (ie, [R ² SiO _3/2 ]), in some embodiments, are predominantly linked together to form a branched polymer chain, which is referred to as a “non-linear block”. Called. In some embodiments, a significant number of these non-linear blocks are further aggregated to form "nanodomains", providing a block copolymer in solid form. In some embodiments, these nanodomains form a separate phase from the phase formed from the linear blocks with D units, and thus form a resin-rich phase. In some embodiments, disiloxy unit _^[R 1 _{2 SiO 2/2]} is 10 to 400 amino disiloxy unit on average per linear block _^[R 1 _{2 SiO 2/2]} (e.g., average About 10 to about 350 D units, about 10 to about 300 D units, about 10 to about 200 D units, about 10 to about 100 D units, about 50 to about 400 D units, about 100 to about 400 D units, about 150 to about 400 D units, about 200 to about 400 D units, about 300 to about 400 D units, about 50 to about 300 D units, about 100 to about 300 D units, about 150 to about 300 D units, about 200 to about 300 D units, about 100 to about 150 D units, about 115 to about 125D units are arranged in a linear block with about 90 to about 170D units, or from about 110 to about 140D units), Torishirokishi units ^[R 2 S O _3/2] are arranged in non-linear block having a molecular weight of at least 500 g / mol, at least 30% of the non-linear blocks are crosslinked with each other.

  In some embodiments, the non-linear block is at least 500 g / mol, for example, at least 1000 g / mol, at least 2000 g / mol, at least 3000 g / mol, at least 4000 g / mol, at least 5000 g / mol, at least 6000 g / mol. Having a number average molecular weight of at least 7000 g / mol or at least 8000 g / mol, or about 500 g / mol to 8000 g / mol, about 500 g / mol to 7000 g / mol, about 500 g / mol to 6000 g / mol, about 500 g / mol. About 5000 g / mol, about 500 g / mol to about 4000 g / mol, about 500 g / mol to about 3000 g / mol, about 500 g / mol to about 2000 g / mol, about 500 g / mol to about 1000 g / mol, about 1000 g / mol. 2000g / mo About 1000 g / mol to about 1500 g / mol, about 1000 g / mol to about 1200 g / mol, about 1000 g / mol to about 3000 g / mol, about 1000 g / mol to about 2500 g / mol, about 1000 g / mol to about 4000 g / mol, About 1000 g / mol to 5000 g / mol, about 1000 g / mol to 6000 g / mol, about 1000 g / mol to 7000 g / mol, about 1000 g / mol to 8000 g / mol, about 2000 g / mol to about 3000 g / mol, about 2000 g / mol. It has a molecular weight of from about 4000 g / mol, from about 2000 g / mol to 5000 g / mol, from about 2000 g / mol to 6000 g / mol, from about 2000 g / mol to 7000 g / mol, or from about 2000 g / mol to 8000 g / mol.

  In some embodiments, at least 30% of the non-linear blocks are cross-linked to each other, for example, at least 40% of the non-linear blocks are cross-linked to each other, and at least 50% of the non-linear blocks are % Are cross-linked to each other, at least 60% of the non-linear blocks are cross-linked to each other, at least 70% of the non-linear blocks are cross-linked to each other, or at least 80% of the non-linear blocks. The percentages are cross-linked to one another, wherein all percentages given herein to indicate the percentage of cross-linked non-linear blocks are weight percentages. In other embodiments, about 30% to about 80% of the non-linear blocks are cross-linked to each other, and about 30% to about 70% of the non-linear blocks are cross-linked to each other. About 30% to about 60% of the blocks are cross-linked to each other, about 30% to about 50% of the non-linear blocks are cross-linked to each other, and about 30% to about 40% of the non-linear blocks are Cross-linked to each other, about 40% to about 80% of the non-linear blocks are cross-linked to each other, and about 40% to about 70% of the non-linear blocks are cross-linked to each other, About 40% to about 60% of the blocks are cross-linked to each other, about 40% to about 50% of the non-linear blocks are cross-linked to each other, and about 50% to about 80% of the non-linear blocks are About 50% to about 70% of the non-linear blocks are cross-linked to each other and non-linear About 55% to about 70% of the blocks are cross-linked to each other, about 50% to about 60% of the non-linear blocks are cross-linked to each other, and about 60% to about 80% of the non-linear blocks are Cross-linked to each other, or about 60% to about 70% of the non-linear blocks are cross-linked to each other.

  Crosslinking of the non-linear block may be achieved via various chemical mechanisms and / or moieties. For example, crosslinking of non-linear blocks within the block polymer may result from condensation of residual silanol groups present within the non-linear blocks of the copolymer.

In some embodiments, the organosiloxane block copolymer of the embodiments described herein, the 40 to 90 mole percent formula _^[R 1 _{2 SiO 2/2]} disiloxy units, e.g., 50 to 90 mole percent formula _^[R 1 _{2 SiO 2/2]} disiloxy units, disiloxy unit of the formula _^[R 1 _{2 SiO 2/2]} of 60-90 mole percent, the formula of 65-90 mole percent _^[R 1 _{2 SiO 2/2]} disiloxy unit disiloxy unit, or disiloxy unit of the formula _^[R 1 _{2 SiO 2/2]} of 80-90 mole percent of 70 to 90 mole percent formula _^[R 1 _{2 SiO 2/2]} of 40 to 80 mole percent disiloxy unit of the formula _^[R 1 _{2 SiO 2/2]} a, castles of formula _^[R 1 _{2 SiO 2/2]} from 40 to 70 mole percent Alkoxy units, disiloxy units of formula 40 to 60 mole percent _^[R 1 _{2 SiO 2/2],} disiloxy unit of 40 to 50 mole percent formula ^{_{[R 1 2 SiO 2/2],}} 50~80 mole percent of formula ^[R ₁ 2 _{SiO 2/2]} disiloxy units, 50-70 mole percent formula _^[R 1 _{2 SiO 2/2]} disiloxy units, 50 to 60 mole percent formula _^[R 1 _{2 SiO 2/2]} disiloxy unit, disiloxy unit of formula 60-80 mole percent _^[R 1 _{2 SiO 2/2],} of 60 to 70 mole percent formula _^[R 1 _{2 SiO 2/2]} disiloxy units, or 70-80 mole percent including disiloxy unit of the formula _^[R 1 _{2 SiO 2/2].}

In some embodiments, the organosiloxane block copolymer of the embodiments described herein, Torishirokishi units 10 to 60 mole percent of the formula ^[R _{2 SiO 3/2],} for example, 10 to 20 mole percent of formula Torishirokishi units ^[R 2 _{SiO 3/2],} Torishirokishi units 10 to 30 mole percent of the formula ^[R _{2 SiO 3/2],} of 10 to 35 mole percent formula ^[R _{2 SiO 3/2]} Torishirokishi units, Torishirokishi units 10 to 40 mole percent of the formula ^[R _{2 SiO 3/2],} Torishirokishi units of the formula of 10 to 50 mole percent ^[R _{2 SiO 3/2],} wherein 20 to 30 mole percent ^[R 2 SiO _{3 /} Torishirokishi units _2, Torishirokishi units 20 to 35 mole percent of the formula ^[R _{2 SiO 3/2]} Torishirokishi units 20 to 40 mole percent of the formula ^[R _{2 SiO 3/2],} Torishirokishi units of the formula 20 to 50 mole percent ^[R _{2 SiO 3/2],} wherein 20 to 60 mole percent ^[R 2 SiO _{3 /} Torishirokishi units _2, Torishirokishi units 30 to 40 mole percent of the formula ^[R _{2 SiO 3/2],} Torishirokishi units of the formula 30 to 50 mole percent ^[R _{2 SiO 3/2],} 30 to 60 mole percent formula Torishirokishi units ^[R _{2 SiO 3/2],} of 40 to 50 mole percent wherein Torishirokishi units ^[R _{2 SiO 3/2],} or 40 to 60 mole percent of the formula ^[R _{2 SiO 3/2]} of Contains trisiloxy units.

The organosiloxane block copolymers of the embodiments described herein may contain additional siloxy units, such as M siloxy units, Q siloxy units, or other unique D or T siloxy units (eg, organic groups other than R ¹ or R ^2). Having an siloxane group), provided that the organosiloxane block copolymer contains a mole fraction of disiloxy and trisiloxy units as described herein, and from about 0.5 to about 5 mole% ( For example, about 0.5 to about 1 mole%, about 0.5 to about 4.5 mole%, about 1 to about 4 mole%, about 2 to about 3 mole%, about 2 to about 4 mole%, about 1 to about 4 mole%. to about 5 mole% or about 2 to about 5 mol%), provided that comprises a C ₁ -C ₃₀ hydrocarbyl group containing at least one aliphatic unsaturation.

  In some embodiments, the resin-linear organosiloxane block copolymer also contains silanol groups (≡SiOH). The amount of silanol groups present in the organosiloxane block copolymer may be from 0.5 to 35 mole percent silanol groups [@SiOH], or from 2 to 32 mole percent silanol groups [@SiOH], or from 8 to 22 mole percent silanol. Groups [@SiOH], or 10-20 mole percent silanol groups [@SiOH], or 15-20 mole percent silanol groups [@SiOH], or 12-22 mole percent silanol groups [@SiOH], or 15 It may vary from ２５25 mole percent silanol groups [≡SiOH], or from 15 to 35 mole percent silanol groups [≡SiOH], or from 1 to 35 mole percent silanol groups. Silanol groups may be present on any siloxy unit in the organosiloxane block copolymer. The amounts described herein represent the total amount of silanol groups found in the organosiloxane block copolymer. In some embodiments, a majority of the silanol groups (eg, greater than 75%, greater than 80%, greater than 90%, about 75% to about 90%, about 80% to about 90%, or about 75% to about 85%). %) Will be present on the trisiloxy units, ie, the resin component of the block copolymer. Without being bound by any theory, the silanol groups present in the resin component of the organosiloxane block copolymer allow the block copolymer to further react or cure at elevated temperatures.

Each R ¹ , as described herein, is independently a C ₁ -C ₃₀ hydrocarbyl (eg, a C ₁ -C ₂₀ hydrocarbyl, a C ₁ -C ₁₀ hydrocarbyl or a C ₁ -C ₆ hydrocarbyl). The hydrocarbyl group may be free of aliphatic unsaturation and may independently be an alkyl, aryl or alkylaryl group. Each R ¹ may be independently a C ₁ -C ₃₀ alkyl group, or each R ¹ may be a C ₁ -C ₁₈ alkyl group, respectively. Alternatively, each R ¹ may be a C ₁ -C ₆ alkyl group such as methyl, ethyl, propyl, butyl, pentyl, or hexyl, respectively. Alternatively, each R ¹ may each be methyl. Each R ¹ may be an aryl group such as a phenyl group, a naphthyl group, or an anthryl group. Alternatively, each R ¹ can each be any combination of the above alkyl or aryl groups, such that in some embodiments, each disiloxy unit has two alkyl groups (eg, two alkyl groups). A methyl group), two aryl groups (for example, two phenyl groups), or one alkyl group (for example, methyl) and one aryl group (for example, phenyl). Alternatively, the organosiloxane block copolymer comprises about 0.5 to about 5 mole% (e.g., about 0.5 to about 1 mole%, about 0.5 to about 4.5 mole%, about 1 to about 4 mole%, about 1 to about 4 mole%, 2 to about 3 mol%, about 2 to about 4 mol%, about 1 to about 5 mol% or about 2 to about 5 mol%) of C ₁ -C ₃₀ hydrocarbyl groups containing at least one aliphatic unsaturated bond. Each R ¹ may be phenyl or methyl, respectively.

In some embodiments, each R ¹ , as described herein, is independently a C ₁ -C ₃₀ hydrocarbyl, wherein the hydrocarbyl group contains at least one aliphatic unsaturated bond. . Examples of aliphatic unsaturated bonds include, but are not limited to, alkenyl or alkynyl bonds. In some embodiments, the aliphatic unsaturation is a terminal double bond. C ₂ -C _{30 (e.g., C 2 ~C 20, C 2} ~C 12, C 2 ~C 8, or _C 2 -C ₄₎ Examples of hydrocarbyl groups include, but are not limited _{to, H} 2 C _{= CH-, H 2 C = CHCH} 2 -, H 2 C = C (CH 3) CH 2 -, H 2 C = CHC (CH 3) 2 -, H 2 C = CHCH 2 CH 2 -, H 2 C _{= CHCH 2 CH 2 CH 2 -} , H 2 C = CHCH 2 CH 2 CH 2 CH 2 - and the like. Other examples of C ₂ -C ₃₀ hydrocarbyl group, but are not limited _{to, HC≡C-, HC≡CCH 2 -, HC≡CCH} (CH 3) -, HC≡CC (CH 3) 2 - and _{HC≡CC (CH 3) 2 CH 2} - and the like. Alternatively, ^{R 1} is a vinyl _group, a H 2 C = CH-.

Each R ² , as described herein, is independently a C ₁ -C ₃₀ hydrocarbyl (eg, a C ₁ -C ₂₀ hydrocarbyl, a C ₁ -C ₁₀ hydrocarbyl or a C ₁ -C ₆ hydrocarbyl). The hydrocarbyl group may be free of aliphatic unsaturation and may independently be an alkyl, aryl or alkylaryl group. Each R ² may be independently a C ₁ -C ₃₀ alkyl group, or each R ² may be each a C ₁ -C ₁₈ alkyl group. Alternatively, each R ² may be a C ₁ -C ₆ alkyl group such as methyl, ethyl, propyl, butyl, pentyl, or hexyl, respectively. Alternatively, each R ² may each be methyl. Each R ² may be an aryl group such as a phenyl group, a naphthyl group, or an anthryl group. Alternatively, each R ² can each be any combination of the alkyl or aryl groups described above, eg, in some embodiments, each disiloxy unit has two alkyl groups (eg, two methyl groups). Group), two aryl groups (eg, two phenyl groups), or one alkyl group (eg, methyl) and one aryl group (eg, phenyl). Alternatively, about 0.5 to about 5 mole% (e.g., about 0.5 to about 1 mole%, about 0.5 to about 4.5 mole%, about 1 to about 4 mole%, about 1 to about 4 mole%) of the organosiloxane block copolymer. 2 to about 3 mol%, about 2 to about 4 mol%, about 1 to about 5 mol% or about 2 to about 5 mol%) of C ₁ -C ₃₀ hydrocarbyl groups containing at least one aliphatic unsaturated bond. Each R ² may be phenyl or methyl, respectively.

In some embodiments, each R ² , as described herein, is independently a C ₁ -C ₃₀ hydrocarbyl, wherein the hydrocarbyl group comprises at least one aliphatic unsaturated bond. , Terms are as defined herein.

As used throughout this specification, “hydrocarbyl” also includes substituted hydrocarbyl groups. "Substituted," as used throughout this specification, replaces one or more of the hydrogen atoms in the group with a substituent known to those of skill in the art to provide a stable compound as described herein. Broadly refers to causing. Examples of suitable substituents include, but are not limited to, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, alkaryl, hydroxy, alkoxy, aryloxy, carboxy (ie, CO ₂ H), carboxyalkyl, carboxy Aryl, cyano, cyanate ester (ie, -OCN group), silyl, siloxy, phosphine, halogen, sulfur-containing group, nitro, epoxy (two adjacent carbon atoms together with the oxygen atom to which it is attached Which forms a group). Substituted hydrocarbyls also include halogen-substituted hydrocarbyls, where the halogen may be fluorine, chlorine, bromine, or a combination thereof.

The organosiloxane block copolymer of the embodiments described herein may have a weight average molecular weight (M _w ) of at least 20,000 g / mol, alternatively a weight average molecular weight of at least 40,000 g / mol, or at least 50,000 g / mol. It has a weight average molecular weight, or at least 60,000 g / mol, or at least 80,000 g / mol, or at least 100,000 g / mol. In some embodiments, the organosiloxane block copolymer described herein comprises from about 20,000 g / mol to about 250,000 g / mol, from about 40,000 g / mol to about 250,000 g / mol, about 50 g / mol. A weight average molecular weight (M _w ) of from 2,000 g / mol to about 250,000 g / mol or from about 100,000 g / mol to about 250,000 g / mol, or a weight of from about 45,000 g / mol to about 100,000 g / mol. Average molecular weight, or weight average molecular weight of about 50,000 gmol to about 100,000 g / mol, or weight average molecular weight of about 50,000 g / mol to about 80,000 g / mol, or about 50,000 g / mol to about 70 gmol A weight average molecular weight of 20,000 g / mol, or a weight average molecular weight of about 50,000 g / mol to about 60,000 g / mol. Having a molecular weight. In some embodiments, the organosiloxane block copolymer of the embodiments described herein comprises from about 15,000 to about 50,000 g / mol, from about 15,000 to about 30,000 g / mol, about 20,000. Has a number average molecular weight ( _Mn ) of from about 20,000 to about 30,000 g / mol, or from about 20,000 to about 25,000 g / mol. Average molecular weight can be readily determined using gel permeation chromatography (GPC) techniques, such as those described in the examples.
Method for producing organosiloxane block copolymer

In some embodiments, the resin-linear organosiloxane block copolymer of the embodiments of the present invention comprises:
A) A resin linear organosiloxane block copolymer,
Disiloxy unit of the formula _^[R 1 _{2 SiO 2/2]} of 40 to 90 mole percent,
Torishirokishi units of the formula ^[R _{2 SiO 3/2]} of 10 to 60 mole percent,
From 0.5 to 35 mole percent silanol groups [@SiOH];
Where:
Each R ¹ is independently C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation;
Each R ² is independently a C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation;
here,
The disiloxy unit _^[R 1 _{2 SiO 2/2]} are arranged in linear blocks having an average per linear block 10-400 amino disiloxy unit _^[R 1 _{2 SiO 2/2]} ,
The trisiloxy units [R ² SiO _3/2 ] are arranged in non-linear blocks having a molecular weight of at least 500 g / mol, at least 30% of the non-linear blocks being cross-linked to one another,
Each linear block is linked to at least one non-linear block via a -Si-O-Si- bond, and
The organosiloxane block copolymer is a resin-linear organosiloxane block copolymer having a weight average molecular weight of at least 20,000 g / mol.
B) a compound of formula ^R 1 ^R _{2 2} SiX,
Wherein each R ¹ is independently a C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation or a C ₁ -C ₃₀ hydrocarbyl group containing at least one aliphatic unsaturated bond;
Each R ² is independently a C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation or a C ₁ -C ₃₀ hydrocarbyl group containing at least one aliphatic unsaturated bond;
X ^is a -OR 4, F, Cl, Br , I, -OC (O) R 4, -N (R 4) 2, or a hydrolyzable group selected from -ON = ^CR _{4 2,} Wherein R ⁴ may be prepared by contacting (eg, reacting) with a compound that is hydrogen or an optionally substituted C ₁ -C ₆ alkyl group.

In another embodiment, the resin-linear organosiloxane block copolymer of the present embodiments is
A) Formula:
There linear organosiloxanes having ^{_{R 1 3-p (E)}} p SiO (R 1 2 SiO 2/2) n Si (E) p R 1 3-p,
Wherein each R ¹ is independently C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation;
n is 10 to 400;
E ^is a -OR 4, F, Cl, Br , I, -OC (O) R 4, -N (R 4) 2, or a hydrolyzable group selected from -ON = ^CR _{4 2,} Wherein R ⁴ is hydrogen or a C ₁ -C ₆ alkyl group;
Each p is independently 1, 2 or 3, a linear organosiloxane;
B) Unit formula:
Containing ^{_{[R 1 2 R 2 SiO 1/2}} ] a [R 1 R 2 SiO 2/2] b [R 1 SiO 3/2] c [R 2 SiO 3/2] d [SiO 4/2] e An organosiloxane resin,
Wherein each R ¹ is independently a C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation or a C ₁ -C ₃₀ hydrocarbyl group containing at least one aliphatic unsaturated bond;
Each R ² is independently a C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation or a C ₁ -C ₃₀ hydrocarbyl group containing at least one aliphatic unsaturated bond;
The organosiloxane resin contains 0 to 35 mol% of silanol groups [≡SiOH], and the subscripts a, b, c, d, and e represent the mole fraction of each siloxy unit present in the organosiloxane resin. Rate, the range of which is
a is from about 0 to about 0.6;
b is about 0 to about 1;
c is from about 0 to about 1,
d is about 0 to about 1,
e is from about 0 to about 0.6;
However, b + c + d + e> 0 and a + b + c + d + e ≦ 1 may be prepared by a method including a step of reacting with an organosiloxane resin.

In yet another embodiment, the resin-linear organosiloxane block copolymer of the embodiments of the present invention comprises:
A) Formula:
There linear organosiloxanes having ^{_{R 1 3-p (E)}} p SiO (R 1 2 SiO 2/2) n Si (E) p R 1 3-p,
Wherein each R ¹ is independently C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation;
n is 10 to 400;
E ^is a -OR 4, F, Cl, Br , I, -OC (O) R 4, -N (R 4) 2, or a hydrolyzable group selected from -ON = ^CR _{4 2,} Wherein R ⁴ is hydrogen or a C ₁ -C ₆ alkyl group;
Each p is independently 1, 2 or 3, a linear organosiloxane;
B) Unit formula:
Containing ^{_{[R 1 2 R 2 SiO 1/2}} ] a [R 1 R 2 SiO 2/2] b [R 1 SiO 3/2] c [R 2 SiO 3/2] d [SiO 4/2] e An organosiloxane resin,
Wherein each R ¹ is independently C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation;
Each R ² is independently a C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation;
The organosiloxane resin contains 0 to 35 mol% of a silanol group [≡SiOH], and
Subscripts a, b, c, d, and e represent the mole fraction of each siloxy unit present in the organosiloxane resin, and the range is
a is from about 0 to about 0.6;
b is from about 0 to about 0.6;
c is from about 0 to about 1,
d is about 0 to about 1,
e is from about 0 to about 0.6;
Where b + c + d + e> 0 and a + b + c + d + e ≦ 1;
C) a compound of the formula R ¹ _q SiX _4-q ,
Wherein each R ¹ is independently a C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation or a C ₁ -C ₃₀ hydrocarbyl group containing at least one aliphatic unsaturated bond;
q is 0, 1, or 2,
Each X is, -OR 4 ^{independently,} F, Cl, Br, I , -OC (O) R 4, -N (R 4) 2, or a hydrolyzable group selected from -ON = ^CR _{4 2} Wherein R ⁴ may be prepared by a method comprising contacting with hydrogen or a compound that is an optionally substituted C ₁ -C ₆ alkyl group,
The "contacting" may be performed in any suitable order. For example, A) and B) may be contacted first, followed by C). Alternatively, A) and C) may be contacted first and then contacted with B), B) and C) may be contacted first and then contacted with A), or A), B) and C) may be contacted with each other substantially simultaneously. In some embodiments, the product of contacting A) and B) is contacted with C).

The method of forming organosiloxane block copolymers described herein includes, in some embodiments,
Disiloxy unit of the formula _^[R 1 _{2 SiO 2/2]} of 40 to 90 mole percent,
Torishirokishi units of the formula ^[R _{2 SiO 3/2]} of 10 to 60 mole percent,
Producing a reaction product that is an organosiloxane block copolymer containing 0.5 to 35 mole percent silanol groups [@SiOH];
Where:
Each R ¹ is independently a C ₁ -C ₃₀ hydrocarbyl or a C ₁ -C ₃₀ hydrocarbyl group containing at least one aliphatic unsaturated bond;
Each R ² is independently a C ₁ -C ₃₀ hydrocarbyl or a C ₁ -C ₃₀ hydrocarbyl group containing at least one aliphatic unsaturated bond;
here,
The disiloxy unit _^[R 1 _{2 SiO 2/2]} are arranged in linear blocks having an average per linear block 10-400 amino disiloxy unit _^[R 1 _{2 SiO 2/2]} ,
The trisiloxy units [R ² SiO _3/2 ] are arranged in a non-linear block having a molecular weight of at least 500 g / mol;
At least 30% of the non-linear blocks are cross-linked to each other;
Each linear block is linked to at least one non-linear block via a -Si-O-Si- bond;
The organosiloxane block copolymer has a weight average molecular weight of at least 20,000 g / mol, and the organosiloxane block copolymer has about 0.5 to about 5 mol% of a C containing at least one aliphatic unsaturated bond. including a _{1 ~C 30} hydrocarbyl group.

In some embodiments, such organosiloxane block copolymer reaction product may be contacted with a compound of the formula ^R ₅ q _{SiX 4-q,} wherein each ^{R 5} is, _C 1 independently -C ₈ A hydrocarbyl (eg, a C ₁ -C ₈ alkyl group, or a phenyl group, or R ⁵ is methyl, ethyl, or a combination of methyl and ethyl) or a C ₁ -C ₈ halogen-substituted hydrocarbyl, wherein each X is independently -OR 4, F ^{and, Cl, Br, I, -OC} (O) R 4, -N (R 4) 2, or a hydrolyzable group selected from -ON = ^CR _{4 2,} wherein Wherein R ⁴ is hydrogen or an optionally substituted C ₁ -C ₆ alkyl group.

In one embodiment, compounds having the formula R 5 q SiX 4-q is an alkyl triacetoxy silane such as methyl triacetoxy silane, ethyltriacetoxysilane, or a combination of the two. Typical commercially available alkyltriacetoxysilanes include ETS-900 (Dow Corning Corp. (Midland, MI)), methyl-tris (methylethylketoxime) silane (MTO), methyltriacetoxysilane, ethyltriacetoxysilane, tetra Examples include acetoxysilane, tetraoximesilane, dimethyldiacetoxysilane, dimethyldioximesilane, and methyltris (methylmethylketoxime) silane. In some embodiments, the organosiloxane block copolymer reaction product is contacted with a compound of the formula R 5 q SiX 4-q, for example, a group which is cured by moisture curing mechanism after the hydrosilylation curing organosiloxane block copolymer May be introduced.
Linear organosiloxane

Wherein ^{_{R 1 3-p (E)}} p SiO (R 1 2 SiO 2/2) n Si (E) p R 1 3-p ( wherein each ^{R 1} is, each independently, an aliphatic unsaturation Not containing C ₁ -C ₃₀ hydrocarbyl, n is 10-400, and E is —OR ⁴ , F, Cl, Br, I, —OC (O) R ⁴ , —N (R ⁴ ) ₂ , or -ON = ^CR ₄ a ₂ hydrolyzable group selected from, wherein, ^{R 4} is a linear organosiloxane having a hydrogen) or a _C 1 -C ₆ alkyl group.

  The subscript "n" may be considered to be the degree of polymerization (dp) of the linear organosiloxane, and may range from 10 to 400 (e.g., about 10 to about 350 D units, about 10 to about 300 D units, about 10 to about 300 D units on average, About 200 D units, about 10 to about 100 D units, about 50 to about 400 D units, about 100 to about 400 D units, about 150 to about 400 D units, about 200 to about 400 D units, about 300 to about 400 D units, about 50 to about 300 D units, about 100 to about 300 D units, about 150 to about 300 D units, about 200 to about 300 D units, about 100 to about 150 D units, about 115 to about 125 D units, about 90 to about 170 D units, or about 110 to about 140 D units. (Unit).

Although organosiloxane having the formula ^{_{R 1 3-p (E)}} p SiO (R 1 2 SiO 2/2) n Si (E) p R 1 3-p are described as linear, those skilled in the art, a straight It is understood that the chain organosiloxane may include a small amount of another siloxy unit, for example, a T (R ¹ SiO _3/2 ) siloxy unit. Similarly, the organosiloxane may be considered to be "predominantly" linear by having a majority of the D (R 1 ² _{SiO 2/2)} siloxy units. Further, the linear organosiloxane may be a combination of a plurality of linear organosiloxanes. Still further, the linear organosiloxane may contain silanol groups. In some embodiments, the linear organosiloxane has about 0.5 to about 5 mole% silanol groups, for example, about 1 mole% to about 3 mole%, about 1 mole% to about 2 mole%, or about It contains from 1 mole% to about 1.5 mole% of silanol groups.
Organosiloxane resin

Unit formula ^{_{[R 1 2 R 2 SiO 1/2}} ] a [R 1 R 2 SiO 2/2] b [R 1 SiO 3/2] c [R 2 SiO 3/2] d [SiO 4/2] e And a method for preparing the same, wherein each R ¹ is independently C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation, and each R ² is independently a C ₁ -C ₃₀ hydrocarbyl free of aliphatic unsaturation) are known in the art. See, for example, WO 2012/040302 and WO 2012/040305, which are hereby incorporated by reference in their entireties. In some embodiments, the above-mentioned organosiloxane resin is prepared by hydrolyzing an organosilane having three hydrolyzable groups such as a halogen or an alkoxy group on a silicon atom in an organic solvent. A representative example for the preparation of a silsesquioxane resin can be found in US Pat. No. 5,075,103. In addition, many organosiloxane resins are commercially available and are sold either as solids (flakes or powders) or dissolved in organic solvents. Suitable non-limiting commercially available organosiloxane resins include Dow Corning® 217 flake resin, 233 flake, 220 flake, 249 flake, 255 flake, Z-6018 flake (Dow Corning Corporation (Midland MI)). Is mentioned.

Unit formula ^{_{[R 1 2 R 2 SiO 1/2}} ] a [R 1 R 2 SiO 2/2] b [R 1 SiO 3/2] c [R 2 SiO 3/2] d [SiO 4/2] e And a method of preparing the same, wherein each R ¹ is independently a C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation or a C ₁ containing at least one aliphatic unsaturated bond. _A C ₁ -C ₃₀ hydrocarbyl group, wherein each R ² is independently a C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation or a C ₁ -C ₃₀ hydrocarbyl group containing at least one aliphatic unsaturated bond. ) May be manufactured in a similar manner.
Compounds of the formula ^R 1 ^R _{2 2} SiX

In some embodiments, the C ₁ -C ₃₀ hydrocarbyl group containing at least one aliphatic unsaturated bond is
Disiloxy unit of the formula _^[R 1 _{2 SiO 2/2]} of 40 to 90 mole percent,
Torishirokishi units of the formula ^[R _{2 SiO 3/2]} of 10 to 60 mole percent,
Resin linear organosiloxane block copolymer containing 0.5 to 35 mole percent silanol groups [@SiOH], where:
Each R ¹ is independently C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation;
Each R ² is independently a C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation;
here,
The disiloxy unit _^[R 1 _{2 SiO 2/2]} are arranged in linear blocks having an average per linear block 10-400 amino disiloxy unit _^[R 1 _{2 SiO 2/2]} ,
The trisiloxy units [R ² SiO _3/2 ] are arranged in non-linear blocks having a molecular weight of at least 500 g / mol, at least 30% of the non-linear blocks being cross-linked to one another,
Each linear block is linked to at least one non-linear block via a -Si-O-Si- bond, and
The organosiloxane block copolymer is at least 20,000 g / mol having a weight average molecular weight) or unit formula ^{_{[R 1 2 R 2 SiO 1/2}} ] a [R 1 R 2 SiO 2/2] b [R 1 SiO _3/2 ] _c [R ² SiO _3/2 ] _d [SiO _4/2 ] _e containing organosiloxane resin
Wherein ^R 1 ^R ₂ 2 SiX compound (wherein, each ^{R 1} is _{independently} a C 1 _{-C 30} hydrocarbyl or at least one _C 1 _{-C 30} hydrocarbyl group containing an aliphatic unsaturated bond, Each R ² is independently a C ₁ -C ₃₀ hydrocarbyl or a C ₁ -C ₃₀ hydrocarbyl group containing at least one aliphatic unsaturated bond, and X is —OR ⁴ , F, Cl, Br, I , ^-OC (O) R 4, an -N ^(R _{4) 2,} or a hydrolyzable group selected from -ON = ^CR _{4 2,} wherein, ^{R 4} is optionally substituted by hydrogen or Or a C ₁ -C ₆ alkyl group)
Is introduced into the organosiloxane block copolymer of an embodiment of the present invention by contacting (eg, reacting).

In one embodiment, the compound of the formula ^R 1 ^R _{2 2} SiX the formula ^(vinyl) _R 2 2 SiX, ^(vinyl) _R 2 2 SiCl, _{(vinyl) (CH 3) 2 SiX,} ( vinyl) _(CH 3) ₂ SiCl, (vinyl) _(phenyl) 2 SiX, (vinyl) _(phenyl) 2 SiCl, (vinyl - ^phenyl) _R 2 2 SiX or (vinyl - ^phenyl) may be a compound of _R 2 2 SiCl.

When used, the amount of the organosilane having the formula ^R 1 ^R _{2 2} SiX may vary, in some embodiments, from about 0.5 to about 20 mole% (e.g., about 0. 5 to about 1 mol%, about 0.5 to about 4.5 mol%, about 1 to about 4 mol%, about 2 to about 3 mol%, about 2 to about 4 mol%, about 1 to about 5 mol% , About 2 to about 5 mol%, about 2 to about 10 mol%, about 5 to about 10 mol%, about 5 to about 15 mol%, about 10 to about 20 mol%, or about 5 to about 20 mol%). is an amount sufficient to provide an organosiloxane block copolymer finally comprising C ₁ -C ₃₀ hydrocarbyl group containing at least one aliphatic unsaturation.
Curable resin-linear organosiloxane block copolymer composition

This disclosure is drawn, inter alia, from about 0.5 to about 5 mole percent of at least one C ₁ -C ₃₀ resin linear organosiloxane block copolymer comprising a hydrocarbyl group and suitable solvents containing aliphatic unsaturated bonds (e.g., A curable composition comprising an aromatic solvent such as benzene, toluene, xylene, or a combination thereof is also provided. The above curable composition has the unit formula:
^{_{[R 1 2 R 2 SiO 1/2}} ] a [R 1 R 2 SiO 2/2] b [R 1 SiO 3/2] c [R 2 SiO 3/2] d have a _{[SiO 4/2] e} And
It may be cured by a hydrosilylation reaction in the presence of a compound containing 0 to 35 mol% of silanol groups [≡SiOH],
Where:
Each R ¹ is independently H or C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation;
Each R ² is independently H or C ₁ -C ₃₀ hydrocarbyl free of aliphatic unsaturation;
The subscripts a, b, c, d, and e represent the mole fraction of each siloxy unit present, and the range is
a is from about 0 to about 0.6;
b is from about 0 to about 0.6;
c is from about 0 to about 1,
d is about 0 to about 1,
e is from about 0 to about 0.6;
However,
b + c + d + e> 0 and a + b + c + d + e ≦ 1;
At least about 1 mol% (e.g., at least about 5 mol%, at least about 10 mol%, at least about 15 mol% or at least about 20 mol%, or about 1 to about 20 mol%, about 1 to about 10 mol% or about R ¹ and / or R ² is H.

This disclosure is drawn, inter alia, from about 0.5 to about 5 mole percent of at least one C ₁ -C ₃₀ resin linear organosiloxane block copolymer comprising a hydrocarbyl group and suitable solvents containing aliphatic unsaturated bonds (e.g., A curable composition comprising an aromatic solvent such as benzene, toluene, xylene, or a combination thereof is also provided. The curable composition has the unit formula:
^{_{[R 1 2 R 2 SiO 1/2}} ] a [R 1 R 2 SiO 2/2] b [R 1 SiO 3/2] c [R 2 SiO 3/2] d have a _{[SiO 4/2] e} And
It may be cured by a hydrosilylation reaction in the presence of a compound containing 0 to 35 mol% of silanol groups [≡SiOH],
Where:
Each R ¹ is independently H, and the formula — [R ⁶ R ⁷ Si] _k [R ⁶ R ⁷ SiH] (wherein R ⁶ and R ⁷ independently represent H or aliphatic unsaturation. a _C 1 _{-C 30} hydrocarbyl free, k is _C 1 _{-C 30} hydrocarbyl containing no silane groups or aliphatic unsaturated and is) an integer of 0,
Each R ² is independently H, and the formula — [R ⁶ R ⁷ Si] _k [R ⁶ R ⁷ SiH] (wherein R ⁶ and R ⁷ independently represent H or aliphatic unsaturation. a _C 1 _{-C 30} hydrocarbyl free, k is _C 1 _{-C 30} hydrocarbyl containing no silane groups or aliphatic unsaturated and is) an integer of 0,
The subscripts a, b, c, d, and e represent the mole fraction of each siloxy unit present, and the range is
a is from about 0 to about 0.6;
b is from about 0 to about 0.6;
c is from about 0 to about 1,
d is about 0 to about 1,
e is from about 0 to about 0.6;
However,
b + c + d + e> 0 and a + b + c + d + e ≦ 1;
At least about 1 mol% (e.g., at least about 5 mol%, at least about 10 mol%, at least about 15 mol% or at least about 20 mol%, or about 1 to about 20 mol%, about 1 to about 10 mol% or about (1 to about 5 mol%) R ¹ and / or R ² is H or a silane group of the formula — [R ⁶ R ⁷ Si] _k [R ⁶ R ⁷ SiH].

In one embodiment, the unit formula ^{_{[R 1 2 R 2 SiO 1/2}} ] a [R 1 R 2 SiO 2/2] b [R 1 SiO 3/2] c [R 2 SiO 3/2] d [SiO compounds with _{4/2] e} is a compound of the formula ^{_{R 1 q R 3 (3-}} q) SiO (R 1 2 SiO 2/2) m SiR 3 (3-q) R 1 q, where Each R ¹ is independently a C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation, and m is 0-50 (eg, about 10 to about 50 D units, about 20 to about 50 D units, about 5 To about 40 D units, or about 10 to about 40 D units), or 0 to 10, or 0 to 5, or m is 0, q is 0, 1, or 2, or q is 2. each _{R 3} is H or ^{R 1} each independently, provided that the formula ^R ₁ q R ^{_{(3-q) SiO (R}} 1 2 SiO 2/2) m SiR 3 (3-q) at least one _{R 3} at each end of the compound of ^R _{1 q} is H.

In some embodiments, the unit formula ^{_{[R 1 2 R 2 SiO 1/2}} ] a [R 1 R 2 SiO 2/2] b [R 1 SiO 3/2] c [R 2 SiO 3/2] d _{[SiO 4/2]} a compound having the _e or the formula ^{_{R 1 q R 3 (3-}} q) SiO (R 1 2 SiO 2/2) m SiR 3 (3-q) compound of ^R _{1 q} has the formula H ( CH ₃ ) ₂ SiO [(CH ₃ ) ₂ SiO _2/2 )] _n Si (CH ₃ ) ₂ H, where n is 10 to 400 (eg, about 10 to about 350 D units on average, about 10 About 300 D units, about 10 to about 200 D units, about 10 to about 100 D units, about 50 to about 400 D units, about 100 to about 400 D units, about 150 to about 400 D units, about 200 to about 400 D units, about 300 to about 400 D units. About 400D units, about 50 to about 300D units, 100 to about 300 D units, about 150 to about 300 D units, about 200 to about 300 D units, about 100 to about 150 D units, about 115 to about 125 D units, about 90 to about 170 D units, or about 110 to about 140 D units. You may.

In a further embodiment, the unit formula ^{_{[R 1 2 R 2 SiO 1/2}} ] a [R 1 R 2 SiO 2/2] b [R 1 SiO 3/2] c [R 2 SiO 3/2] d [ SiO _4/2] a compound having the _e or the formula ^{_{R 1 q R 3 (3-}} q) SiO (R 1 2 SiO 2/2) m SiR 3 (3-q) compound of ^R _{1 q} has the formula H (CH _{3) 2 SiOSi (CH 3)} 2 H, H (CH 3) (Ph) SiOSi (CH 3) 2 H, H (Ph) 2 SiOSi (CH 3) 2 H, H (CH 3) (Ph) SiOSi ( _{CH 3) (Ph) H,} H (Ph) 2 SiOSi (Ph) 2 H, H (CH 3) 2 SiOSi (CH 3) 2 OSi (CH 3) 2 H, H (CH 3) 2 SiOSi (Ph) _{(CH 3) OSi (CH 3} ) 2 H, H (CH 3 _{2 SiOSi (Ph) 2 OSi (} CH 3) 2 H, H (CH 3) (Ph) SiOSi (Ph) (CH 3) OSi (Ph) (CH 3) H, H (CH 3) (Ph) SiOSi ( _Ph) having _{2 OSi (Ph) (CH 3} ) H or _{H (CH 3) 2 SiOSi (} Ph) 2 OSi (Ph) 2 OSi (CH 3) 2 H.

In another embodiment, the curable composition has a unit formula:
It may be cured by a hydrosilylation reaction in the presence of a compound having [R ¹ R ² R ⁸ SiO _1/2 ] _f [R ¹ R ⁹ SiO _2/2 ] _g [R ¹ SiO _3/2 ] _h ,

Wherein R ¹ and R ² are independently C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation, and R ⁸ and R ⁹ are independently H, C containing no aliphatic unsaturation. ₁ -C ₃₀ hydrocarbyl or formula _{^{- [10 R 11 Si R]}} p [R 10 R 11 SiH] ( ^wherein, R ^{10, R 11} is independently _C 1 that does not contain H or aliphatic unsaturation -C _{30 is} hydrocarbyl, p is an integer of 0 to 10), and f is 0 to 100 (for example, 2 to 100, 40 to 50, 40 to 60, 50 to 70, 40 to 80, 40). To 70, 1 to 80, 1 to 10, 0 to 10, 1 to 6, or 10 to 70), and g is 0 to 50 (for example, 1 to 50, 1 to 30, 1 to 8, 1 to 1). 6 or 1 to 4), and h is 0 to 60 (for example, 30 to 50, 0 to 15, 0 to 0). An integer of 0,10～40,20～40,0～10,0～5 or 1-5), unit formula _{^{[R 1 R 2 R 8 SiO}} 1/2] f [R 1 R 9 SiO 2 / ₂ ] _g [R ¹ SiO _3/2 ] The number of SiH groups in the compound having _h is ≧ 2 (for example, ≧ 4, ≧ 6, ≧ 8, ≧ 10, or 2 to 10 per molecule). It is.

Non-compounds having the unit formula [R ¹ R ² R ⁸ SiO _1/2 ] _f [R ¹ R ⁹ SiO _2/2 ] _g [R ¹ SiO _3/2 ] _h (where g is 0) As a limited example,
[R ¹ R ² R ⁸ SiO _1/2 ] _f [R ¹ SiO _3/2 ] _h ,
Wherein R ¹ and R ² are independently C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation, and R ⁸ is independently H, C ₁ -C containing no aliphatic unsaturation. ₃₀ hydrocarbyl or formula _{^{- [10 R 11 Si R]}} p [R 10 R 11 SiH] ( ^wherein, R ^{10, R 11} is a _C 1 _{-C 30} hydrocarbyl independently contains no H or aliphatic unsaturated And p is an integer of 0 to 10), and f is 2 to 100 (for example, 40 to 50, 40 to 60, 50 to 70, 40 to 80, 40 to 70, 2 to 80, H is an integer of 0 to 60 (for example, 30 to 50, 0 to 15, 0 to 40, 10 to 40, 20 to 40, 0 to 10, 0). To 5 or 1 to 5), and has a unit formula of [R ¹ R ² R ⁸ SiO _1/2 ] _f The number of SiH groups in the compound having [R ¹ SiO _3/2 ] _h is ≧ 2 per molecule (eg, ≧ 4, ≧ 6, ≧ 8, ≧ 10, or 2 to 10 per molecule).

Others of compounds having the unit formula [R ¹ R ² R ⁸ SiO _1/2 ] _f [R ¹ R ⁹ SiO _2/2 ] _g [R ¹ SiO _3/2 ] _h (where g is 0) Non-limiting examples of
[R ¹ R ² R ⁸ SiO _1/2 ] _f [R ¹ SiO _3/2 ] _h ,
Wherein R ¹ and R ² are independently C ₁ -C ₁₀ alkyl (eg, C ₁ -C ₈ alkyl, C ₁ -C ₅ alkyl or C ₁ -C ₃ alkyl) or C ₆ -C ₁₄ aryl. (Eg, C ₆ -C ₁₀ aryl), and R ⁸ is independently H or C ₁ -C ₁₀ alkyl (eg, C ₁ -C ₈ alkyl, C ₁ -C ₅ alkyl or C ₁ -C ₃ alkyl). alkyl) or _C 6 _{-C 14} aryl _(e.g., a C 6 _{-C 10} aryl), f is 2 to 100 (e.g., 40～50,40～60,50～70,40～80,40～70, 2 to 80, 2 to 10, 2 to 6 or 10 to 70), and h is 0 to 60 (for example, 30 to 50, 0 to 15, 0 to 40, 10 to 40, 20 to 40, 0). -10, 0-5 or 1-5), and at least two ⁸ is H, the number of SiH groups in the compound having the result unit formula _{^{[R 1 R 2 R 8 SiO}} 1/2] f [R 1 SiO 3/2] h is, ≧ per molecule 2 (e.g. ≧ 4, ≧ 6, ≧ 8, ≧ 10, or 2 to 10) per molecule.

Further addition of the compound having the unit formula [R ¹ R ² R ⁸ SiO _1/2 ] _f [R ¹ R ⁹ SiO _2/2 ] _g [R ¹ SiO _3/2 ] _h (where g is 0) Another non-limiting example is
[R ¹ R ² R ⁸ SiO _1/2 ] _f [R ¹ SiO _3/2 ] _h ,
Wherein R ¹ and R ² are independently C ₁ -C ₃ alkyl or C ₆ -C ₁₀ aryl, and R ⁸ is independently H, C ₁ -C ₃ alkyl or C ₆ -C _10. Aryl, and f is an integer of 2 to 100 (for example, 40 to 50, 40 to 60, 50 to 70, 40 to 80, 40 to 70, 2 to 80, 2 to 10, 2 to 6, or 10 to 70) And h is an integer of 0 to 60 (for example, 30 to 50, 0 to 15, 0 to 40, 10 to 40, 20 to 40, 0 to 10, 0 to 5, or 1 to 5), and at least 2 R ⁸ are H, such that the number of SiH groups in the compound having the unit formula [R ¹ R ² R ⁸ SiO _1/2 ] _f [R ¹ SiO _3/2 ] _h is per molecule ≧ 2 (eg, ≧ 4, ≧ 6, ≧ 8, ≧ 10, or 2 to 10).

Further addition of the compound having the unit formula [R ¹ R ² R ⁸ SiO _1/2 ] _f [R ¹ R ⁹ SiO _2/2 ] _g [R ¹ SiO _3/2 ] _h (where g is 0) Another non-limiting example is
[R ¹ R ² R ⁸ SiO _1/2 ] _f [R ¹ SiO _3/2 ] _h ,
Wherein R ¹ is methyl or phenyl, R ² is methyl or phenyl, R ⁸ is H, and f is 2-100 (eg, 40-50, 40-60, 50-70, 40- 80, 40 to 70, 2 to 80, 2 to 10, 2 to 6, or 10 to 70), and h is 0 to 60 (for example, 30 to 50, 0 to 15, 0 to 40, 10 to 40). , 20 to 40, 0 to 10, 0 to 5 or 1 to 5), so that the number of SiH groups in the cross-linking agent molecule is ≧ 2 per cross-linking agent molecule (for example, one cross-linking agent molecule) ≧ 4, ≧ 6, ≧ 8, ≧ 10, or 2 to 10). Alternatively, in some embodiments, R ¹ is methyl or phenyl, R ² is methyl or phenyl, R ⁸ is H, and e is 40-80 (eg, 40-50, 40-60 or 50 to 70), and g is an integer of 30 to 60. As a result, in the compound having the unit formula [R ¹ R ² R ⁸ SiO _1/2 ] _f [R ¹ SiO _3/2 ] _h Is 2 or more per molecule (eg, ≧ 4, ≧ 6, ≧ 8, ≧ 10, or 2 to 10 per molecule).

Non-compounds having the unit formula [R ¹ R ² R ⁸ SiO _1/2 ] _f [R ¹ R ⁹ SiO _2/2 ] _g [R ¹ SiO _3/2 ] _h (where h is 0) As a limited example,
[R ¹ R ² R ⁸ SiO _1/2 ] _f [R ¹ R ⁹ SiO _2/2 ] _g ,
Wherein R ¹ and R ² are independently C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation, and R ⁸ and R ⁹ are independently H, C containing no aliphatic unsaturation. ₁ -C ₃₀ hydrocarbyl or formula _{^{- [10 R 11 Si R]}} p [R 10 R 11 SiH] ( ^wherein, R ^{10, R 11} is independently _C 1 that does not contain H or aliphatic unsaturation -C _{30 is} hydrocarbyl, p is an integer of 0 to 10), and f is an integer of 0 to 10 (for example, 0 to 9, 1 to 9, 2 to 8, 2 to 6 or 2 to 4). G is an integer of 0 to 10 (for example, 0 to 9, 0 to 7, 0 to 5, ^{1 to 8, 1 to} 6, or 1 to 4), and has the unit formula [R ¹ R ² R ⁸ The number of SiH groups in the compound having [SiO _1/2 ] _f [R ¹ R ⁹ SiO _2/2 ] _g is ≧ 2 per molecule (for example, ≧ 4, ≧ 6, ≧ 8, ≧ 10, or 2 to 10) per molecule.

Others of compounds having the unit formula [R ¹ R ² R ⁸ SiO _1/2 ] _f [R ¹ R ⁹ SiO _2/2 ] _g [R ¹ SiO _3/2 ] _h (where h is 0) Non-limiting examples of
[R ¹ R ² R ⁸ SiO _1/2 ] _f [R ¹ R ⁹ SiO _2/2 ] _g ,
Wherein R ¹ , R ² , and R ⁹ are independently C ₁ -C ₁₀ alkyl (eg, C ₁ -C ₈ alkyl, C ₁ -C ₅ alkyl or C ₁ -C ₃ alkyl) or C _6. -C ₁₄ aryl _(e.g., C 6 _{-C 10} aryl) and, ^{R 8} is independently H or _C 1 _{-C 10} alkyl _(e.g., C 1 -C _{8 alkyl,} C 1 -C ₅ alkyl or C _{1 to} C ₃ alkyl) or C _{6 to} C ₁₄ aryl (for example, C _{6 to} C ₁₀ aryl), and f is an integer of 2 to 10 (for example, 2 to 8, 2 to 6, or 2 to 4). , G is an integer of 0 to 10 (for example, 1 to ⁸ , 1 to 6, or 1 to 4), and at least two R ⁸ are H, so that the unit formula [R ¹ R ² R ⁸ SiO _{^{1/2] f [R 1 R 9}} SiO 2/2] SiH groups in the compound having a _g The number ≧ per molecule 2 (e.g., ≧ per molecule 4, ≧ 6, ≧ 8, ≧ 10, or 2 to 10) is.

Further addition of the compound having the unit formula [R ¹ R ² R ⁸ SiO _1/2 ] _f [R ¹ R ⁹ SiO _2/2 ] _g [R ¹ SiO _3/2 ] _h (where h is 0) Another non-limiting example is
[R ¹ R ² R ⁸ SiO _1/2 ] _f [R ¹ R ⁹ SiO _2/2 ] _g ,
Wherein R ¹ , R ² and R ⁹ are independently C ₁ -C ₃ alkyl or C ₆ -C ₁₀ aryl, and R ⁸ is independently H, C ₁ -C ₃ alkyl or C 9 _{6 to} C ₁₀ aryl, f is an integer of 2 to 10 (for example, 2 to 8, 2 to ₆ , or 2 to 4), and g is 0 to 10 (for example, 0 to 9, 0 to 7, 0). , 5, 1-8, 1-6 or 1-4), and at least two R ⁸ are H, resulting in the unit formula [R ¹ R ² R ⁸ SiO _1/2 ] _f [ R ¹ R ⁹ SiO _2/2 ] _g , the number of SiH groups in the compound having ≧ 2 (for example, ≧ 4, ≧ 6, ≧ 8, ≧ 10, or 2 to 10 per molecule). is there.

Further addition of the compound having the unit formula [R ¹ R ² R ⁸ SiO _1/2 ] _f [R ¹ R ⁹ SiO _2/2 ] _g [R ¹ SiO _3/2 ] _h (where h is 0) Another non-limiting example is
[R ¹ R ² R ⁸ SiO _1/2 ] _f [R ¹ R ⁹ SiO _2/2 ] _g ,
In the formula, R ¹ is methyl or phenyl, R ² is methyl or phenyl, R ⁹ and R ² are methyl or phenyl, R ⁸ is H, and f is 2 to 10 (for example, 2 to 10). 8, 2 to 6 or 2 to 4), and g is an integer of 1 to 10 (for example, 1 to 8, 1 to 6, or 1 to 4). Alternatively, in some embodiments, R ¹ is methyl or phenyl, R ² is methyl or phenyl, R ⁹ , R ² is methyl or phenyl, R ⁸ is H, and f is 2- 10 (for example, 2 to 8, 2 to 6, or 2 to 4), and g is 0 to 10 (for example, 0 to 9, 0 to 7, 0 to 5, 1 to 8, 1 to 6, or 1). To 4).

In some embodiments, the formulas [R ¹ R ² R ⁸ SiO _1/2 ] _f [R ¹ R ⁹ SiO _2/2 ] _g and [R ¹ R ² R ⁸ SiO _1/2 ] _f [R ¹ SiO _3/2 ] _h (eg, ^MH ₂ D ^Ph ₂ and ^MH 60T ^Ph ₄₀ , respectively) are used in various embodiments of the curable compositions of the present invention. Formulas [R ¹ R ² R ⁸ SiO _1/2 ] _e [R ¹ R ⁹ SiO _2/2 ] _f and [R ¹ R ² R ⁸ SiO _1/2 ] _e [R ¹ SiO _3/2 ] _g 2 If a combination of two different compounds is used, the compounds can be used in any suitable amount and in any suitable ratio. In some examples, the formulas [R ¹ R ² R ⁸ SiO _1/2 ] _e [R ¹ R ⁹ SiO _2/2 ] _f and [R ¹ R ² R ⁸ SiO _1/2 ] _e [R ¹ SiO _{3 / 2} ] _g of the two different compounds has a suitable w / w ratio of about 8: 1 to about 1: 8 (eg, about 6: 1 to about 1: 1, about 5: 1 to about 1: 1, About 5: 1 to about 2: 1, or about 5: 1 to about 3: 1 w / w).

  The hydrosilylation reaction may be performed under any suitable conditions known in the art for performing a hydrosilylation reaction.

  The curable composition may contain a hydrosilylation catalyst. The hydrosilylation catalyst may be any suitable hydrosilylation catalyst, such as a Group VIII metal-based catalyst selected from platinum, rhodium, iridium, palladium, ruthenium or iron. Group VIII metal-containing catalysts useful for catalyzing the hydrosilylation reaction are any catalysts known to catalyze the reaction of a silicon-bonded hydrogen atom with a silicon-bonded moiety comprising an unsaturated hydrocarbon group. May be. In some embodiments, the Group VIII metal used as a catalyst to effect hydrosilylation is a platinum-based catalyst such as platinum metal, platinum compounds and platinum complexes.

  Suitable platinum catalysts include U.S. Pat. No. 2,823,218 (e.g., "Speier catalyst") and U.S. Pat. Examples include, but are not limited to, the catalysts described in Patent No. 3,923,705. Other suitable platinum catalysts include, but are not limited to, platinum catalysts referred to as "Karstedt catalysts" described in U.S. Patent Nos. 3,715,334 and 3,814,730. Karstedt's catalyst is a platinum divinyltetramethyldisiloxane complex, optionally containing about 1 weight percent platinum in a solvent such as toluene. Alternatively, platinum catalysts include chloroplatinic acid and terminal chloroplatinic acids, including those described in US Pat. No. 3,419,593, which are incorporated by reference as if fully set forth herein. Examples include, but are not limited to, reaction products with an organosilicon compound containing aliphatic unsaturation. Alternatively, hydrosilylation catalysts include, but are not limited to, neutralized complexes of platinum chloride and divinyltetramethyldisiloxane as described in US Pat. No. 5,175,325. Further suitable hydrosilylation catalysts are described, for example, in U.S. Patent Nos. 3,159,601; 3,220,972; 3,296,291; 3,516,946; Nos. 3,989,668, 4,784,879, 5,036,117, and 5,175,325, and EP 0 347 895 (B1). .

  The hydrosilylation catalyst may be added in an amount corresponding to a small amount of a platinum group metal element of 0.001 parts by weight (ppm) per million parts of the total reaction composition. In some embodiments, the concentration of the hydrosilylation catalyst relative to the solids of the reaction composition is a concentration that is capable of providing at least 1 ppm equivalent of a platinum group metal element. A catalyst concentration that results in a platinum group metal element corresponding to 1-500, alternatively 50-500, or 50-200 ppm may be used.

This disclosure is drawn, inter alia, also a curable composition comprising about 0.5 to about 5 mole percent of C ₁ -C ₃₀ resin linear organosiloxane block copolymer containing hydrocarbyl group containing at least one aliphatic unsaturated bond Provided, wherein the curable composition has a cure rate in Pa / min (the slope of G 'versus time, determined from the rheology of the increase in storage modulus G' as a function of temperature) of 5 ° C / At a heating rate of at least about 1 Pa / min, at least about 2 Pa / min, at least about 4 Pa / min, at least about 10 Pa / min or at least about 20 Pa / min, for example, at a heating rate of 5 ° C./min, about 1 Pa / min. Min to about 10 Pa / min, about 1 Pa / min to about 20 Pa / min, about 1 Pa / min to about 6 Pa / min, about 2 Pa / min to about 6 Pa / min, about 1 Pa / min to about 100 Pa / min. About 5 Pa / min to about 50 Pa / min, about 10 Pa / min to about 100 Pa / min, about 20 Pa / min to about 80 Pa / min, about 20 Pa / min to about 60 Pa / min, about 50 Pa / min to about 100 Pa / min. Or about 30 Pa / min to about 90 Pa / min.
Solid resin-linear organosiloxane block copolymer composition

  The solid composition containing the resin-linear organosiloxane block copolymer of an embodiment of the present invention may comprise some or substantially all solvent from the curable organosiloxane block copolymer composition as described herein. May be prepared by removing The solvent may be removed by any known processing techniques. In one embodiment, a film of the curable composition containing the organosiloxane block copolymer is formed and the solvent is evaporated from the film. Exposure of the film to elevated temperatures and / or reduced pressure may facilitate solvent removal and subsequent formation of a solid curable composition. Alternatively, the curable composition may be passed through an extruder to remove the solvent and obtain a solid composition in the form of a ribbon or pellet. Coating operations on release films can also be used as in the case of slot die coating, knife over roll, rod, or gravure coating. Roll-to-roll coating operations can also be used to prepare solid films. In the coating operation, a conveyor oven or other solution heating and evacuation means may be used to remove the solvent and obtain the final solid film.

Without wishing to be bound by any theory, when the solid composition of the block copolymer is formed, the disiloxy and trisiloxy units in the organosiloxane block copolymer as described herein maintain structural regularity. This can result in copolymers having certain unique physical property characteristics. For example, the structural regularity of disiloxy and trisiloxy units in a copolymer can result in a solid coating that allows for high light transmission of visible light (eg, wavelengths greater than 350 nm). Also, having structural regularity may allow the organosiloxane block copolymer to flow and cure when heated, but to maintain stability at room temperature. These can also be processed using lamination techniques. These properties are useful for improving the weatherability and durability of various electronic articles, while creating coatings to provide energy efficient, low cost and easy procedures. The structural regularity of the disiloxy and trisiloxy units in the copolymer allows for, among other things, glass transition temperatures T _g (the copolymer has a high T _g phase), tackiness (the copolymer has a low tackiness), Affects strength, especially as evidenced by tensile strength, and storage stability.

In some embodiments, the organosiloxane block copolymer described above can be prepared, for example, by casting a film of a solution of the block copolymer in an organic solvent (eg, benzene, toluene, xylene, or a combination thereof) to evaporate the solvent. Separated in solid form. Under these conditions, the organosiloxane block copolymer has a solids content of about 50% to about 80% by weight, for example, about 60% to about 80%, about 70% to about 80% or about 75% by weight. % To about 80% by weight solids. In some embodiments, the solvent is toluene. In some embodiments, such a solution is about 1500 mm ² / s to about 10000 mm ² / s (about 1500cSt~ about 10,000 cSt) at 25 ° C., for example, about at 25 ℃ 1500mm ² / s~ about 3000 mm ² / s, from about 2000 mm ² / s to about 4000 mm ² / s, about 2000 mm ² / s to about 3000 mm ² / s, about 2000 mm ² / s to about 8000mm ² / s, about 5000 mm ² / s to about 10000 mm ² / s or about 8000mm ² / s to about 10000 mm ² / s (about 1500cSt~ about 3000 cSt, about 2000cSt~ about 4000CSt, about 2000cSt~ about 3000 cSt, about 2000cSt~ about 8000CSt, about 5000cSt~ about 10,000 cSt, or about 8000cSt~ about 10,000 cSt) May be provided.

  In some embodiments, the cured product of a curable composition containing a resin-linear organosiloxane block copolymer of an embodiment of the present invention has a 50 hour aging at 225 ° C. after aging at 225 ° C. for 50 hours. It has a Young's modulus that is not substantially different from the Young's modulus before aging. In some embodiments, the ratio of the Young's modulus after aging at 225 ° C. for 50 hours to the Young's modulus before aging is 3 or less (eg, about 2.5 or less, about 2.0 or less, or about 2 hours after aging). 1.5 or less; or about 1 to about 2.5, about 1.25 to about 2, about 1.5 to about 1.8 or about 1.4 to about 2.25, if the ratio is 1, The Young's modulus before and after aging is understood to be the same).

  In some embodiments, the cured product of a curable composition containing a resin-linear organosiloxane block copolymer of an embodiment of the present invention is aged at 225 ° C. for 30 hours after aging at 225 ° C. for 30 hours. It has a Young's modulus that is not substantially different from the Young's modulus before aging. In some embodiments, the Young's modulus after aging at 225 ° C. for 30 hours is 1.5 or less relative to the Young's modulus before aging (eg, about 1.4 or less after aging, about 1.3 or less, or About 1.2 or less; or about 0 to about 1.5, about 0.5 to about 1.5, about 1.0 to about 1.5 or about 1.0 to about 1.5 after aging, wherein the ratio is If 1, the Young's modulus before and after aging is understood to be the same).

  In some embodiments, the cured product of the curable composition containing the resin-linear organosiloxane block copolymer of an embodiment of the present invention has a Young's modulus before aging at 225 ° C. for 30 or 50 hours. About 70 MPa to about 200 MPa before aging (e.g., about 70 MPa to 100 MPa, about 100 MPa to about 150 MPa, about 120 MPa to about 180 MPa, about 150 MPa to about 180 MPa, or about 130 MPa to about 180 MPa).

  In some embodiments, the Young's modulus after aging at 225 ° C. for 30 hours does not substantially change. When the Young's modulus changes after aging at 225 ° C. for 30 hours, the Young's modulus after aging is about 100 MPa to about 250 MPa after aging at 225 ° C. for 30 hours (eg, about 100 MPa to about 150 MPa, about 150 MPa to about 180 MPa, About 130 MPa to 180 MPa, about 100 MPa to about 140 MPa, or about 140 MPa to about 180 MPa).

  In some embodiments, the Young's modulus after aging at 225 ° C. for 50 hours does not substantially change. When the Young's modulus changes after aging at 225 ° C. for 50 hours, the Young's modulus after aging is about 130 MPa to about 250 MPa after aging at 225 ° C. for 50 hours (eg, about 130 MPa to about 200 MPa, about 150 MPa to about 250 MPa, About 180 MPa to 240 MPa, about 150 MPa to about 240 MPa, or about 180 MPa to about 250 MPa).

  In some embodiments, the cured product of a curable composition containing a resin-linear organosiloxane block copolymer of an embodiment of the present invention may be cured in the absence of a condensation catalyst. In another embodiment, the cured product of the curable composition containing the resin-linear organosiloxane block copolymer of the present invention is cured and cured in the presence of a phosphor or filler. Representative examples of suitable phosphors and fillers are found in PCT Application No. PCT / US2013 / 031253.

  Upon drying or formation of the solid, the non-linear blocks of the block copolymer further aggregate together to form "nanodomains." As used herein, “predominantly agglomerated” refers to the majority (eg, greater than 50%, greater than 60%, greater than 75%, greater than 80%, 90%) of the non-linear blocks of the organosiloxane block copolymer. Greater than, about 75% to about 90%, about 80% to about 90%, or about 75% to about 85%) are found in certain regions of the solid composition (referred to herein as "nanodomains"). Means that As used herein, a “nanodomain” is a phase region in a solid block copolymer composition that is phase separated within the solid block copolymer composition and has at least one dimension that is between 1 and 100 nanometers in size. Point to. The shape of the nanodomain can vary, provided that the size of at least one dimension of the nanodomain is between 1 and 100 nanometers. Thus, nanodomains can be of regular or irregular shape. Nanodomains may be spherical, tubular, and optionally lamellar.

In a further embodiment, the solid organosiloxane block copolymer described herein comprises a first phase and an incompatible second phase, wherein the first phase is primarily composed of disiloxy units [R ¹² ₂ SiO _2/2 ], the second phase mainly contains trisiloxy units [R ² SiO _3/2 ] according to the definition of the present application, and the non-linear blocks are fully agglomerated, It becomes a nanodomain that is incompatible with one phase.

  In some embodiments, the resin-linear organosiloxane block copolymer of embodiments of the present invention may further contain an organosiloxane resin (eg, a free resin that is not part of the block copolymer). In this example, the organosiloxane resin also aggregates predominantly within the nanodomain. In some embodiments, the free resin is present in an amount of about 5% to about 30%, preferably about 10% to about 30% by weight.

  The structural regularity of the disiloxy and trisiloxy units in the solid block copolymers of the present disclosure, as well as the characteristics of the nanodomains, are determined by transmission electron microscopy (TEM), atomic force microscopy (AFM), small angle neutron scattering. , Can be explicitly measured using certain analytical techniques such as X-ray small angle scattering and scanning electron microscopy.

  Alternatively, the structural regularity of the disiloxy and trisiloxy units within the block copolymer, as well as the formation of nanodomains, can be shown by characterizing certain physical properties of the coating resulting from the organosiloxane block copolymer of the present invention. For example, the organosiloxane copolymers of the present invention can result in coatings having visible light transmission greater than 95%. One skilled in the art will recognize that such optical clarity is only possible because visible light can pass through such media (besides the two phases having matching refractive indices), and 150 nm It is understood that only if not diffracted by particles (or domains as used herein) having a larger particle size. As the particle size or domain becomes smaller, the optical clarity can be further improved. Thus, coatings or encapsulants derived from the organosiloxane copolymers of the present invention have a visible light transmission of at least 95%, for example, at least 96%, at least 97%, at least 98%, at least 99%, or 100% visible light. Light transmission may be provided in the coating or encapsulant or film with a film thickness of 0.5 mm or more. As used herein, the term "visible light" includes light of wavelengths greater than 350 nm.

  Some embodiments of the present invention are directed to optical assemblies and articles comprising the compositions described herein, such as WO 2013/101675 (filed December 2, 2012); WO 2013/109607. No. (filed Jan. 16, 2013); those described in WO 2013/119796 (filed Feb. 7, 2013), all of which are as if fully set forth herein. , Incorporated by reference. Accordingly, some embodiments of the present invention relate to LED encapsulants that include the organosiloxane block copolymers described herein.

  As used herein, the term "about" allows for a degree of variation in the value or range, for example, within 10%, 5%, or 1% of the stated value or range limit. be able to.

  A value expressed in a range format is not limited to only the numerical value explicitly stated as the limit of the range, but to all values subsumed within that range as if each numerical value and subrange were explicitly stated. Should be interpreted flexibly to include individual values or subranges of. For example, a range of "about 0.1% to about 5%" or "about 0.1% to 5%" includes not only about 0.1% to about 5%, but also individual numbers within the indicated range. Values (e.g., 1%, 2%, 3%, and 4%) and subranges (e.g., 0.1% -0.5%, 1.1% -2.2%, 3.3% -4) .4%).

  The embodiments of the invention described and claimed herein are not limited to the specific embodiments disclosed herein, since these embodiments are intended to be illustrative of some aspects of the present disclosure. The scope should not be limited. Any equivalent embodiments are intended to be within the scope of the present disclosure. Indeed, various modifications of the embodiments in addition to those shown and described herein will become apparent to those skilled in the art from the foregoing description. Such modifications are also intended to fall within the scope of the appended claims.

  The Abstract has been provided so that the reader may quickly ascertain the nature of the technical disclosure. The Abstract has been submitted with the understanding that it will not be used to interpret or limit the scope or objectives of the claims.

The following examples are included to demonstrate certain embodiments of the present invention. However, one of ordinary skill in the art, in light of the present disclosure, may make many changes in the specific embodiments disclosed and still have the same or similar results without departing from the spirit and scope of the invention. It should be understood that All percentages are percentages by weight. All measurements were performed at 23 0 C unless otherwise noted.
Example 1 Representative Preparation of a Resin-Linear (RL) Block Copolymer

To a 12 L three neck round bottom flask was charged phenyl-T resin (1800 g, 13.18 mol Si, Dow Corning 217 flakes) and toluene (1482 g) under nitrogen. The flask was equipped with a thermometer, a Teflon stirring paddle, and a Dean Stark apparatus attached to a water-cooled condenser (the Dean Stark was pre-filled with toluene). The reaction mixture was heated at reflux for 30 minutes to remove 8.18 g of water. After the reaction solution was cooled to 108 ° C., silanol-terminated PhMe siloxane (50/50 wt% MTA / ETA (methyltriacetoxysilane / ethyltriethyl) was sealed with MTA / ETA (methyltriacetoxysilane / ethyltriacetoxysilane). Acetoxysilane) (46.96 g, 0.207 mol Si) was added to the siloxane (2200 g, 16.13 mol Si, DP = 127; where "DP" represents the degree of polymerization determined by NMR) and a glove box (Synthesized by stirring at room temperature for 1 hour). The reaction mixture was heated at reflux under nitrogen for 2 hours to remove 14.66 g of water. The reaction solution was cooled again to 108 ° C., 50/50% by weight of MTA / ETA (methyltriacetoxysilane / ethyltriacetoxysilane) (314.49 g, 1.348 mol) was added, and the mixture was refluxed for 1 hour. 0.56 g of water was removed, then the reaction mixture was cooled to 90 ° C., deionized (DI) water (430 g) was added and then refluxed to remove water by azeotropic distillation. The above water addition-removal process was repeated twice to remove a total of 1045.9 g of aqueous phase. Finally, the solids content of the solution was increased to about 70% by weight by distillation and removal of some volatiles (1331.4 g) at 118 ° C. The synthesized RL solution was clear and colorless and was stored at room temperature for later use.
Example 2: Preparation of ^MVi resin-linear block copolymer with 3.5 mol% Vi

In a 1 L dry, three-necked round bottom flask, a solution of the resin-linear block copolymer prepared according to Example 1 (100 g, 0.77 mol Si, 0.138 mol silanol) in toluene (150 g) and triethylamine ( TEA, 5.76 mL, 0.0414 mol) was added under nitrogen, followed by stirring for 10 minutes. Vinyldimethylchlorosilane (5.7 mL, 0.0414 mol) was added slowly to the flask via syringe within 10 minutes. Within one minute after the addition of the chlorosilane, a white salt precipitate formed. The reaction mixture was stirred at room temperature under nitrogen for 3 hours, followed by addition of 1 mL of DI water to quench unreacted chlorosilane. Finally, 5 g of anhydrous Na ₂ SO ₄ was added to the flask, followed by stirring overnight under air to dry the solution completely. On the second day, the reaction solution was filtered at 138 kPa (20 psi) using 1.2 μm filter paper to remove white salt precipitate. The solvent and a small amount of TEA and the quenched vinyl precursor were completely removed using a Rotavapor at 80 ° C. and a vacuum of 667 kPa (5 mmHg). The ^MVi RL product is a soft, colorless, gum-like material containing 3.5 mol% Vi and can be redissolved in toluene.
Example 3: Preparation of ^MVi modified resin having 2 mol% Vi-linear block polymer

(I) Preparation of M ^Vi _0.045 T ^Ph _0.955 resin: To a 3 L 3-neck round bottom flask was added DI water (1011.9 g), followed by cooling to 4 ° C. in an ice water bath. The flask was equipped with a thermometer, a Teflon stirring paddle, and a water-cooled condenser. A premixed solution of phenyltrichlorosilane (500.5 g, 2.366 mol), vinyldimethylchlorosilane (15.03 g, 0.125 mol) and toluene (494.4 g) was added to the above cooled water within 2 minutes. Addition was followed by removal from the ice-water bath and stirring for 5 minutes (the maximum temperature of the solution during the reaction was 74 ° C. or less). The reaction mixture was transferred to a 2 L round bottom flask with a bottom drain, followed by removal of the aqueous phase. DI water (82.4 g) was added to the residual material, followed by heating at 80 ° C. for 10 minutes, followed by cooling and removal of the aqueous phase. To the residual material was added a mixture of 2-propanol (20.6 g) and DI water (61.8 g), followed by heating at 80 ° C. for 10 minutes to remove the aqueous phase, and combining this step with the final wash water It was repeated several times until the pH of the phase was 4.0. The reaction mixture was then heated to reflux and residual water was removed by azeotropic distillation. The synthesized M ^Vi _0.045 T ^Ph _0.955 resin was dried at 120 ° C. using rotavapor. The ^MVi _0.045 T ^Ph _0.955 product was a "crisp" solid at room temperature, yielding 314 g and containing 4.5 mol% Vi.

(Ii) Preparation of M ^Vi RLs (2 mol% Vi): In a 500 mL four-necked round bottom flask, add M ^Vi _0.045 T ^Ph _0.955 resin (72 g, 0.541 mol Si) and toluene (59.3 g). ) Was placed under nitrogen. The flask was equipped with a thermometer, a Teflon stirring paddle, and a Dean Stark apparatus attached to a water-cooled condenser (the Dean Stark was pre-filled with toluene). The reaction mixture was heated at reflux for 30 minutes to remove 0.01 g of water. After cooling the reaction solution to 108 ° C., silanol-terminated PhMe siloxane (MTA / ETA (50/50, 1.85 g, 0.00813 mol Si) was sealed with MTA / ETA (methyltriacetoxysilane / ethyltriacetoxysilane). ) Was added to siloxane (88 g, 0.645 mol Si, DP = 129), which was synthesized by stirring at room temperature in a glove box for 1 hour. The reaction mixture was heated at reflux under nitrogen for 2 hours to remove 0.65 g of water. The reaction solution was cooled again to 108 ° C., MTA / ETA (50/50, 4.92 g, 0.0216 mol Si) was added, and then refluxed for 1 hour to remove 0.25 g of water. Was cooled to 90 ° C., DI water (8.05 g) was added, then refluxed to remove water by azeotropic distillation. This addition and removal of water was repeated three times. Finally, the solids content of the solution was increased to about 70% by weight by distillation and removal of some volatiles (39.2 g) at 118 ° C. The synthesized M ^Vi RLs solution was clear and colorless and contained 2 mol% Vi.
Example 4: Preparation of ^MVi modified resin having 3.7 mol% Vi-linear block polymer

  (I) M^Vi _0.078T^Ph _0.922Preparation of resin: To a 3 L 3-neck round bottom flask was added DI water (1011.9 g), followed by cooling to 4 ° C. in an ice water bath. The flask was fitted with a thermometer, a Teflon stirring paddle, and a water-cooled condenser. A premixed solution of phenyltrichlorosilane (500.5 g, 2.366 mol), vinyldimethylchlorosilane (26.55 g, 0.22 mol) and toluene (508.5 g) was added to the cooled water within 2 minutes. Addition was followed by removal from the ice-water bath and stirring for 5 minutes (the maximum temperature of the solution during the reaction was 71 ° C. or less). The reaction mixture was transferred to a 2 L round bottom flask with a bottom drain, followed by removal of the aqueous phase. DI water (84.8 g) was added to the residual material, followed by heating at 80 ° C. for 10 minutes, followed by cooling and removal of the aqueous phase. To the residual material was added a mixture of 2-propanol (21.2 g) and DI water (63.6 g), followed by heating at 80 ° C. for 10 minutes to remove the aqueous phase, and this step was repeated in the final wash water. This was repeated several times until the pH of the phase was 4.0. The reaction mixture was then heated to reflux and residual water was removed by azeotropic distillation. Synthesized M^ViPhThe resin was dried at 120 ° C. using rotavapor. The product was a crisp solid at room temperature, yield 332 g and contained 7.8 mol% Vi.

(Ii) Preparation of M ^Vi RL (3.7 mol% Vi): In a 500 mL four-necked round bottom flask, _add M ^Vi _0.078 T ^Ph _0.922 resin (72 g, 0.547 mol Si) and toluene (59). .3 g) under nitrogen. The flask was equipped with a thermometer, a Teflon stirring paddle, and a Dean Stark apparatus attached to a water-cooled condenser (the Dean Stark was pre-filled with toluene). The reaction mixture was heated at reflux for 30 minutes to remove 0.05 g of water. After the reaction solution was cooled to 108 ° C., silanol-terminated PhMe siloxane (MTA / ETA (50/50, 1.85 g, 0.00813 mol Si)) sealed with MTA / ETA was added to siloxane (88 g, 0.645 mol Si , DP = 129), which was synthesized by stirring for 1 hour in a glove box at room temperature). The reaction mixture was heated at reflux under nitrogen for 2 hours to remove 0.7 g of water. The reaction solution was cooled again to 108 ° C., MTA / ETA (50/50, 4.98 g, 0.0219 mol Si) was added, and then refluxed for 1 hour to remove 0.3 g of water. Was cooled to 90 ° C., DI water (8.12 g) was added, then refluxed to remove water by azeotropic distillation. This addition and removal of water was repeated three times. Finally, the solids content of the solution was increased to about 70% by weight by distillation and removal of some volatiles (38.4 g) at 118 ° C. The synthesized M ^Vi RL solution was clear and colorless and contained 3.7 mol% Vi.
Example 5: Preparation of ^DVi modified resin with 3.7 mol% Vi-linear block polymer

(I) Preparation of D ^Vi _0.08 T ^Ph _0.92 resin: To a 3 L 3-neck round bottom flask was added DI water (1011.9 g), followed by cooling to 4 ° C. in an ice water bath. The flask was fitted with a thermometer, a Teflon stirring paddle, and a water-cooled condenser. A premixed solution of phenyltrichlorosilane (500.5 g, 2.366 mol), vinylmethyldichlorosilane (31.04 g, 0.22 mol) and toluene (506.1 g) was added to the above-mentioned cooled water within 2 minutes. And stirred for 5 minutes after removing from the ice-water bath (the maximum temperature of the solution during the reaction was 75 ° C. or less). The reaction mixture was transferred to a 2 L round bottom flask with a bottom drain, followed by removal of the aqueous phase. DI water (84.8 g) was added to the residual material, followed by heating at 80 ° C. for 10 minutes, followed by cooling and removal of the aqueous phase. To the residual material was added a mixture of 2-propanol (21.2 g) and DI water (63.6 g), followed by heating at 80 ° C. for 10 minutes to remove the aqueous phase, and this step was repeated in the final wash water. This was repeated several times until the pH of the phase was 4.0. The reaction mixture was then heated to reflux and residual water was removed by azeotropic distillation. The synthesized D ^Vi T ^Ph resin was dried at 120 ° C. using rotavapor. The product was a crisp solid at room temperature, yield 335 g and contained 8 mol% Vi.

(Ii) Preparation of D ^Vi RL (3.7 mol% Vi): In a 500 mL four-necked round bottom flask, D ^Vi _0.08 T ^Ph _0.92 resin (72 g, 0.55 mol Si) and toluene ( 59.3 g) were charged under nitrogen. The flask was equipped with a thermometer, a Teflon stirring paddle, and a Dean Stark apparatus attached to a water-cooled condenser (the Dean Stark was pre-filled with toluene). The reaction mixture was heated at reflux (113 ° C.) for 30 minutes to remove 0.03 g of water. After the reaction solution was cooled to 108 ° C., silanol-terminated PhMe siloxane (MTA / ETA (50/50, 1.85 g, 0.00813 mol Si)) sealed with MTA / ETA was added to siloxane (88 g, 0.645 mol Si , DP = 129), which was synthesized by stirring for 1 hour in a glove box at room temperature). The reaction mixture was heated at reflux under nitrogen for 2 hours to remove 0.7 g of water. The reaction solution was cooled again to 108 ° C., MTA / ETA (50/50, 1.25 g, 0.0055 mol Si) was added, and the mixture was refluxed for 1 hour to remove 0.27 g of water. Was cooled to 90 ° C., DI water (7.37 g) was added and then refluxed to remove water by azeotropic distillation. This addition and removal of water was repeated three times. Finally, the solids content of the solution was increased to about 70% by weight by distillation and removal of some volatiles (38.3 g) at 118 ° C. The synthesized D ^Vi RL solution was clear and colorless and contained 3.7 mol% Vi.
Example 6: Preparation of ^DVi modified resin with 3.5 mol% Vi-linear block polymer

A 500 mL four-neck round bottom flask was charged with phenyl-T resin (72 g, 0.527 mol Si, Dow Corning 217 flakes) and toluene (59.3 g) under nitrogen. The flask was equipped with a thermometer, a Teflon stirring paddle, and a Dean Stark apparatus attached to a water-cooled condenser (the Dean Stark was pre-filled with toluene). The reaction mixture was heated at reflux (113 ° C.) for 30 minutes to remove 0.1 g of water. After the reaction solution was cooled to 108 ° C., silanol-terminated PhMe siloxane (MTA (methyltriacetoxysilane, 1.79 g, 0.00813 mol Si)) sealed with MTA was replaced with siloxane (88 g, 0.645 mol Si, DP = 129), which was synthesized by stirring for 1 hour in a glove box at room temperature). The reaction mixture was heated at reflux under nitrogen for 2 hours to remove 0.95 g of water. The reaction solution was cooled again to 108 ° C., VMDA (vinyl methyl diacetoxysilane, 8.14 g, 0.0432 mol Si) was added, and the mixture was refluxed for 1 hour to remove 0.65 g of water. Was cooled to 90 ° C., DI water (17.14 g) was added, then refluxed to remove water by azeotropic distillation. The reaction solution was cooled again to 108 ° C., MTA (2.67 g, 0.0121 mol Si) was added and refluxed for 1 hour, then the reaction mixture was cooled to 90 ° C. and DI water (17.14 g) Was added and then refluxed to remove water by azeotropic distillation (this addition-removal of water was repeated twice). Finally, the solids content of the solution was increased to about 70% by weight by distillation and removal of some volatiles (36.5 g) at 118 ° C. The synthesized D ^Vi RL solution was clear and colorless and contained 3.5 mol% Vi.
Example 7: Preparation of ^TVi modified resin with 4.5 mol% Vi-linear block polymer

A 500 mL four-neck round bottom flask was charged with phenyl-T resin (72 g, 0.527 mol Si, Dow Corning 217 flakes) and toluene (59.3 g) under nitrogen. The flask was equipped with a thermometer, a Teflon stirring paddle, and a Dean Stark apparatus attached to a water-cooled condenser (the Dean Stark was pre-filled with toluene). The reaction mixture was heated at reflux (113 ° C.) for 30 minutes to remove 0.1 g of water. After cooling the reaction solution to 108 ° C., silanol-terminated PhMe siloxane (MTA / ETA (50/50, 1.85 g, 0.00813 mol Si)) sealed with MTA was replaced with siloxane (88 g, 0.645 mol Si, DP = 129), which was synthesized by stirring for 1 hour in a glove box at room temperature). The reaction mixture was heated at reflux under nitrogen for 2 hours to remove 0.94 g of water. The reaction solution was cooled again to 108 ° C., and after adding VTA (vinyltriacetoxysilane, 12.84 g, 0.0553 mol Si), the mixture was refluxed for 1 hour to remove 0.71 g of water. Upon cooling to 90 ° C., DI water (17.14 g) was added, then refluxed to remove water by azeotropic distillation. This addition and removal of water was repeated three times to remove a total of 59.1 g of water. Finally, the solids content of the solution was increased to about 70% by weight by distillation and removal of some volatiles (38.6 g) at 118 ° C. The synthesized T ^Vi RL solution was clear and colorless and contained 4.5 mol% Vi.
Example 8: Preparation of ^DVi modified resin with 1 mol% Vi-linear block polymer

A 500 mL four-neck round bottom flask was charged with phenyl-T resin (72 g, 0.535 mol Si, Dow Corning 217 flakes) and toluene (59.3 g) under nitrogen. The flask was equipped with a thermometer, a Teflon stirring paddle, and a Dean Stark apparatus attached to a water-cooled condenser (the Dean Stark was pre-filled with toluene). The reaction mixture was heated at reflux (113 ° C.) for 30 minutes to remove 0.01 g of water. After the reaction solution was cooled to 108 ° C., silanol-terminated PhMe siloxane (MTA (methyltriacetoxysilane, 1.79 g, 0.00813 mol Si)) sealed with MTA was replaced with siloxane (88 g, 0.645 mol Si, DP = 129), which was synthesized by stirring for 1 hour in a glove box at room temperature). The reaction mixture was heated at reflux under nitrogen for 2 hours to remove 0.67 g of water. The reaction solution was cooled again to 108 ° C., VMDA (vinyl methyl diacetoxysilane, 2.33 g, 0.0124 mol Si) was added, and the mixture was refluxed for 1 hour to remove 0.24 g of water. Was cooled to 90 ° C., DI water (14 g) was added, then refluxed to remove water by azeotropic distillation. The reaction solution was cooled again to 108 ° C., MTA (1.77 g, 0.00804 mol Si) was added and refluxed for 1 hour, then the reaction mixture was cooled to 90 ° C. and DI water (15.4 g) Was added and then refluxed to remove water by azeotropic distillation (this addition-removal of water was repeated twice). Finally, the solids content of the solution was increased to about 70% by weight by distillation and removal of some volatiles (31.5 g) at 118 ° C. The synthesized D ^Vi RL solution was clear and colorless and contained 1 mol% Vi.
Example 9: Preparation of ^DVi modified resin with 2 mol% Vi-linear block polymer

A 500 mL four-neck round bottom flask was charged with phenyl-T resin (180 g, 1.318 mol Si, Dow Corning 217 flakes) and toluene (138.6 g) under nitrogen. The flask was equipped with a thermometer, a Teflon stirring paddle, and a Dean Stark apparatus attached to a water-cooled condenser (the Dean Stark was pre-filled with toluene). The reaction mixture was heated at reflux for 30 minutes to remove 0.54 g of water. After cooling the reaction solution to 108 ° C., silanol-terminated PhMe siloxane sealed with MTA / ETA (50/50 MTA / ETA (methyltriacetoxysilane / ethyltriacetoxysilane, 4.24 g, 0.0187 mol Si) Was added to siloxane (220 g, 1.614 mol Si, DP = 181), which was synthesized by stirring at room temperature in a glove box for 1 hour. The reaction mixture was heated at reflux under nitrogen for 2 hours to remove 2.01 g of water. The reaction solution was cooled again to 108 ° C., VMDA (vinyl methyl diacetoxysilane, 11.91 g, 0.0633 mol Si) was added, and the mixture was refluxed for 1 hour to remove 1.05 g of water. Was cooled to 90 ° C., DI water (47.8 g) was added, then refluxed to remove water by azeotropic distillation. The reaction solution was cooled again to 108 ° C., 50/50 MTA / ETA (21.57 g, 0.0949 mol Si) was added and refluxed for 1 hour, then the reaction mixture was cooled to 90 ° C. and DI Water (47.8 g) was added and then refluxed to remove water by azeotropic distillation (this addition-removal of water was repeated twice). The same water treatment was performed three times, and finally the solids content of the solution was increased to about 70% by weight by distillation and removal of some volatiles (103.6 g) at 118 ° C. The synthesized D ^Vi RL solution was clear and colorless and contained 2 mol% Vi.
Example 10: D ^Vi RL with 2 mol% Vi and 1 ppm Pt catalyst

Example 10 was prepared using the D ^Vi RL of Example 9 with 1 ppm of Pt catalyst.
Example 11: T ^Vi RL with 2 mol% ^Vi

A 500 mL four-neck round bottom flask was charged with phenyl-T resin (180 g, 1.318 mol Si, Dow Corning 217 flakes) and toluene (148.2 g) under nitrogen. The flask was equipped with a thermometer, a Teflon stirring paddle, and a Dean Stark apparatus attached to a water-cooled condenser (the Dean Stark was pre-filled with toluene). The reaction mixture was heated at reflux for 30 minutes to remove 1.05 g of water. After cooling the reaction solution to 108 ° C., silanol terminated PhMe siloxane sealed with MTA / ETA (50/50 MTA / ETA (methyltriacetoxysilane / ethyltriacetoxysilane, 4.43 g, 0.0195 mol Si) Was added to siloxane (220 g, 1.614 mol Si, DP = 181), which was synthesized by stirring at room temperature in a glove box for 1 hour. The reaction mixture was heated at reflux under nitrogen for 2 hours to remove 2.05 g of water. The reaction solution was cooled again to 108 ° C. and after adding VTA (vinyltriacetoxysilane, 14.29 g, 0.0615 mol Si) and 50/50 MTA / ETA (14.48 g, 0.0637 mol Si) Refluxed for 1 hour, then cooled the reaction mixture to 90 ° C., added DI water (39.1 g) and then refluxed to remove water by azeotropic distillation. The water treatment (39.1 g DI water) was repeated two more times. Finally, the solids content of the solution was increased to about 70% by weight by distillation and removal of some volatiles (113 g) at 118 ° C. The synthesized D ^Vi RL solution was clear and colorless and contained 2 mol% Vi.
Example 12: Hydrosilylation cured formulation

Resins produced in accordance with Examples 2 to 11 - containing linear organosiloxane block copolymers, hydrosilylation cured formulation, the amounts shown in Table 2 of the resin linear organosiloxane block copolymer, wherein R ¹ _q R ³ _{( ^{3-q) SiO (R 1}} 2 SiO 2/2) m SiR 3 (3-q) compounds with ^R _{1 q,} and were prepared to contain Pt catalyst. The resin-linear organosiloxane block copolymer was prepared as a 60% by weight solution in toluene, which was then poured into Teflon-coated aluminum pans to make 0.5-2 mm thick films. After leaving the aluminum pan in the hood overnight to remove the solvent toluene, a clear, solid, uncured film was uniformly formed in the aluminum pan. The bread containing the solid film was heated in an oven at 70 ° C. for several hours, followed by 120 ° C. for 1 hour, and finally at 160 ° C. for 3 hours to obtain a cured film.
Comparative Example 1:

To a 12 L three neck round bottom flask was charged phenyl-T resin (1800 g, 13.18 mol Si, Dow Corning 217 flakes) and toluene (1482 g) under nitrogen. The flask was equipped with a thermometer, a Teflon stirring paddle, and a Dean Stark apparatus attached to a water-cooled condenser (the Dean Stark was pre-filled with toluene). The reaction mixture was heated at reflux for 30 minutes to remove 8.18 g of water. After the reaction solution was cooled to 108 ° C., silanol-terminated PhMe siloxane (50/50 wt% MTA / ETA (methyltriacetoxysilane / ethyltriethyl) was sealed with MTA / ETA (methyltriacetoxysilane / ethyltriacetoxysilane). Acetoxysilane) (49.96 g, 0.207 mol Si) was added to siloxane (2200 g, 16.13 mol Si, DP = 127), and the mixture was stirred at room temperature in a glove box for 1 hour. ) Was added quickly. The reaction mixture was heated at reflux under nitrogen for 2 hours to remove 14.66 g of water. The reaction solution was cooled again to 108 ° C., and 50/50 wt% MTA / ETA (methyltriacetoxysilane / ethyltriacetoxysilane) (314.49 g, 1.348 mol) was added. .56 g of water was removed, then the reaction mixture was cooled to 90 ° C., deionized (DI) water (430 g) was added, and then refluxed to remove water by azeotropic distillation. The above water addition-removal process was repeated twice to remove a total of 1045.9 g of aqueous phase. Finally, the solids content of the solution was increased to about 70% by weight by distillation and removal of some volatiles (1331.4 g) at 118 ° C. The synthesized resin-linear solution was colorless and transparent. The above resin-linear block copolymer was cured in the presence of 50 ppm DBU to obtain a DBU cured resin-linear solid composition.
Comparative Example 2:

The resin linear solution was synthesized using the same procedure as that shown in Comparative Example 1. To prepare an Al-cured resin-linear solid composition, the above resin-linear block copolymer was cured in the presence of Al (acac) ₃ containing 100 ppm Al.
Comparative Example 3:

The components described below are mixed using a vacuum planetary mixer, Thinky ARV-310, under 2 kPa at 1600 rpm for 2 minutes to form a liquid composition.
Component 1: average unit molecular formula: (Me ₂ ViSiO _1/2 ) _0.25 (PhSiO _3/2 ) _0.75 ; 5.8 g;
Component 2: average unit molecular formula: Me ₂ ViSiO (MePhSiO) ₂₅ OSiMe ₂ Vi; 1.8 g;
Component 3: average unit molecular formula: HMe ₂ SiO (Ph ₂ SiO) SiMe ₂ H; 2.0 g;
Component 4: average unit molecular formula: (HMe ₂ SiO _1/2 ) _0.60 (PhSiO _3/2 ) _0.4 ; 0.24 g;
Component 5: Average unit molecular formula:
(Me ₂ ViSiO _1/2 ) _0.18 (PhSiO _3/2 ) _0.54 (EpMeSiO) _0.28 , wherein (Ep = glycidoxypropyl); 0.23 g;
Component 6: average unit molecular formula: cyclic (ViSiMeO _1/2 ) _n ; 0.02 g;
1-ethynyl-1-cyclohexanol, 240 ppm; and Pt catalyst (1.3-divinyltetramethylsiloxane complex); 2.5 ppm.
Comparative Example 4: Preparation of ^MVi modified resin-linear block polymer with 2.7 mol% Vi by hydrosilylation reaction

(I) Preparation of M ^Vi _0.147 T ^Ph _0.853 resin: To a 3 L 3-neck round bottom flask was added DI water (1011.9 g), followed by cooling to 4 ° C. in an ice water bath. The flask was fitted with a thermometer, a Teflon stirring paddle, and a water-cooled condenser. A premixed solution of phenyltrichlorosilane (444.26 g, 2.1 mol), vinyldimethylchlorosilane (48.26 g, 0.4 mol) and toluene (481.5 g) was added to the cooled water over 3 minutes. Addition (the maximum temperature of the solution during the reaction was 71 ° C. or less), and then immediately removed the ice water bath and heated at 80 ° C. for 15 minutes. The reaction mixture was transferred to a 2 L round bottom flask with a bottom drain and the aqueous phase was removed followed by heating again at 80 ° C. for 15 minutes to promote molecular weight build-up. To the residual material was added DI water (80.25 g), then heated at 80 ° C. for 10 minutes, then cooled and the aqueous phase was removed. A mixture of 2-propanol (20.06 g) and DI water (60.19 g) was added to the residual material, followed by heating at 80 ° C. for 10 minutes to remove the aqueous phase (this step was performed with the final wash water). It was repeated several times until the pH of the phase was 4.0). The reaction mixture was then heated to reflux and residual water was removed by azeotropic distillation. The synthesized M ^Vi _0.147 T ^Ph _0.853 resin was dried at 120 ° C. using a rotary evaporator. The product was a "crisp" solid at room temperature, yield 332 g, and contained 14.7 mol% Vi.

(Ii) Preparation of SiH-terminated PhMe siloxane (DP = 129, ^MH ₂ D ^Ph ₁₂₉ ): 10.8 L of silanol-terminated PhMe siloxane (D ^Ph ₁₂₉ (OH) ₂ in a dry three-necked round bottom flask. 2.207 mol Si, 0.0265 mol silanol), toluene (450 g) and triethylamine (TEA, 4.47 mL, 0.032 mol) were charged under nitrogen and then stirred for 10 minutes. Dimethylchlorosilane (3.53 mL, 0.0318 mol) was added slowly to the flask via syringe within 10 minutes. Within one minute after the addition of the chlorosilane, a white salt precipitate formed. The reaction mixture was stirred at room temperature under nitrogen for 3 hours, followed by addition of 1 mL of DI water to quench unreacted chlorosilane. Finally, 10 g of anhydrous Na ₂ SO ₄ was added to the flask, followed by stirring overnight under air to dry the solution completely. On the second day, the reaction solution was filtered at 207 kPa (30 psi) using 1.2 μm filter paper to remove white salt precipitates. The solvent and a small amount of TEA and the quenched vinyl precursor were completely removed using a Rotavapor at 80 ° C. and a vacuum of 667 kPa (5 mmHg). The ^MH ₂ D ^Ph ₁₂₉ product is a high viscosity, colorless, transparent liquid material.

(Iii) Preparation of M ^Vi RLs ^SysD (2.7 mol% Vi): In a 500 mL four-necked round bottom flask, _add M ^Vi _0.147 T ^Ph _0.853 resin (72 g, 0.56 mol Si), ^MH ₂ D ^Ph ₁₂₉ (88g) and toluene (59.3 g) were placed under nitrogen. The flask was equipped with a thermometer, a Teflon stirring paddle, and a Dean Stark apparatus attached to a water-cooled condenser (the Dean Stark was pre-filled with toluene). The reaction mixture was heated to 90 ° C., followed by the addition of Pt catalyst (TSA-276, 4 g, 2.5 ppm Pt based on total solids weight). The reaction mixture was heated at reflux for 2.5 hours, during which time an IR of the sample was taken to observe the consumption of SiH. The reaction was complete after 2 hours of reflux and 0.63 g of water was removed. The reaction solution was cooled to 108 ° C., followed by, SiH terminated siloxane ^{M H D Ph2 M H (7.46g} , 0.0224 mol) was added and refluxed for 2 hours. The reaction was complete after 2 hours and 0.31 g of water was removed (IRH observation of SiH). Finally, the solids content of the solution was increased to about 60% by weight by distillation and removal of some volatiles at 118 ° C. The synthesized 60% M ^Vi RLs ^SysD solution was colorless, transparent and viscous and contained 2.7 mol% Vi.

Some physical and chemical properties of the resin-linear organosiloxane prepared according to Examples 2-11 are shown in Table 1 below.

^＊ Ｋａｒｓｔｅｄｔ触媒、及び２：３の比のＰｔ：ビニル（ＣＨ_３）_２ＳｉＯＳｉ（ＣＨ_３）_２ビニルを含有全試料で［ＳｉＨ］／［Ｖｉ］＝１
「Ｎ／Ａ」は、データが得られなかったことを示す。 The novel compositions described above, including the resin-linear organosiloxane of embodiments of the present invention, all have greater than 1 mole percent vinyl functionality and mole percent silanol. This allows not only a single cure with vinyl, for example using Si-H hydrosilylation, but also a double cure with, for example, vinyl / Si-H and SiOH / SiOH condensation.

^* [SiH] / [Vi] = 1 for all samples containing Karstedt's catalyst and Pt: vinyl (CH ₃ ) ₂ SiOSi (CH ₃ ) ₂ vinyl in a 2: 3 ratio.
"N / A" indicates that no data was obtained.

The cure rate data shown in Table 2 shows that the resins prepared according to Examples 2-11-resins in which the linear organosiloxane block copolymer can only be cured by condensation in the presence of DBU or Al (acac) ₃ catalyst- It shows cure rates comparable to those observed with linear organosiloxane block copolymers. See data for Comparative Examples 1 and 2. Further, all of the resin-linear organosiloxane block copolymers prepared according to Examples 2-11 show faster cure rates than the resinous linear organosiloxane block copolymer prepared according to the method described in Comparative Example 2.

Resin-linear organosiloxane block copolymers prepared according to Examples 2-11 are curable when containing a phosphor (eg, Ce: YAG used at 50% by weight or less based on total solids). there were. Further, the resin-linear organosiloxane block copolymer prepared according to Examples 2-11 has a storage stability of at least 15 weeks at room temperature (ie, 25 ° C.) and standard pressure (1 atm), The change in G ′ _min is less than about 50% at 15 weeks (eg, less than about 25%, less than about 20%, less than about 15%, less than about 10%, less than about 5%, about 3%, about 0%, (From about 0% to about 50%, from about 3% to about 25%, from about 5% to about 20%, or from about 15% to about 45%). In contrast, the resin-linear organosiloxane block copolymer prepared according to Comparative Example 4 showed a change in G ′ _min of greater than 200% in 15 weeks, and the resin-linear organosiloxane prepared according to Comparative Example 3 The siloxane block copolymer showed a change in G ′ _min of over 1300% in one week. The above results demonstrate that the resin-linear organosiloxane block copolymers of embodiments of the present invention achieve superior storage stability over other materials known in the art that are cured by hydrosilylation. Demonstrate. See, for example, Comparative Example 3.

^＊表３に示すｂ^＊値は、ＢＹＫ比色計を使用して、厚さ約１ｍｍの試料から得た。
「Ｎ／Ａ」は、データが得られなかったことを示す。 Resin-linear organosiloxane block copolymer resin-linear organosiloxane block copolymer prepared according to Examples 2-11 and Comparative Examples 1-4 (before and after aging), Young's modulus data (before aging) And tan δ data are shown in Table 3.

^* B ^* values shown in Table 3 were obtained from a sample about 1 mm thick using a BYK colorimeter.
"N / A" indicates that no data was obtained.

The data shown in Table 3 shows that the resin-linear organosiloxane block copolymer prepared according to an embodiment of the present invention has a CIE b ^* value ratio of 10 before and after aging at 235 ° C. for 72 hours. Less than (e.g., less than about 9, less than about 8, less than about 7, less than about 6, or less than about 5 after aging at 235C for 72 hours, or from about 2 to about 10, after aging at 235C for 72 hours. 3 to about 9, or about 5 to about 10). Resin-linear organosiloxane block copolymers prepared according to certain embodiments of the present invention have a CIE b ^* value ratio of less than 30 before and after aging at 235 ° C. for 72 hours (eg, aging). Less than about 25, less than about 20, or less than about 15; or about 14 times to about 30 times, 15 times to about 20 times, or about 20 times to about 30 times the color change after aging at 235 ° C. for 72 hours. ). In contrast, resin-linear organosiloxane block copolymers prepared according to Comparative Examples 2 and 3 have an unacceptable value of about 50 CIE b ^* values before and after aging at 235 ° C. for 72 hours. Show. In some embodiments, the resin-linear organosiloxane block copolymer prepared according to certain embodiments of the present invention, after aging at 235 ° C. for 72 hours, has a CIE b ^* value of about 6 or less (eg, about 6 or less, about 5 or less, about 4 or less or about 3 or less, or about 3 to about 6 or about 4 to about 6).

^＊Ｒ_ΔＧ’：２２５℃で５００時間のエージングの前及び後に２３℃で測定した弾性率の変化率 The data shown in Table 3 shows that the resin-linear organosiloxane block copolymer prepared according to certain embodiments of the present invention has an acceptable high Young's modulus at room temperature before aging and the resin-linear organosiloxane It also did not show that the Young's modulus changed significantly after aging, such as the siloxane block copolymer becoming brittle after aging.

^* R _{ΔG '} : _Percent change in modulus measured at 23 ° C before and after aging at 225 ° C for 500 hours.

The data shown in Table 4 show that resin-linear organosiloxane block copolymers prepared according to certain embodiments of the present invention show high thermal stability even after 500 hours of thermal aging at 225 ° C. Show. Low 500 hours after the elastic modulus change ^rate, the change in the ^{b *} value of ^D Vi RL is small, the thermal ^stability, indicating that ^D Vi RL is an advantage over ^M Vi RL or ^T Vi RL .

  One significant advantage of the resin-linear organosiloxane block copolymer prepared according to certain embodiments of the present invention is that the tendency for benzene elimination is significantly and surprisingly low when the T group comprises phenyl. It is. In some embodiments, the resin-linear organosiloxane block copolymer produced in accordance with certain embodiments of the present invention has less than 200 ppm of benzene after 30 minutes at 180 ° C. (eg, less than 150 ppm after 30 minutes at 180 ° C.) Less than 125 ppm, less than 100 ppm, less than 75 ppm, less than 50 ppm, less than 25 ppm, less than 20 ppm, less than 15 ppm, less than 10 ppm, or less than 6 ppm benzene, or about 0 ppm to about 200 ppm, about 10 ppm to about 100 ppm after 30 minutes at 180 ° C. About 25 ppm to about 100 ppm, about 2 to about 20 ppm, about 10 ppm to about 20 ppm, or about 10 to about 18 ppm of benzene).

  Another significant advantage of resin-linear organosiloxane block copolymers produced in accordance with certain embodiments of the present invention is that typical condensation catalyst cured resin-linear organosiloxane block copolymers, e.g., Compared to Examples 1 and 2, the tendency to undergo phosphor inhibition after curing is significantly and surprisingly low. Furthermore, the curing rate of the resin-linear organosiloxane block copolymer is much less affected by the phosphor dosage, for example, the initial curing temperature does not change with varying phosphor dosage. For example, the change in the initial temperature of cure (defined in the temperature scan as the temperature at which G ′ increases after the initial drop at the temperature corresponding to the melt flow) is less than 50 ° C., less than 40 ° C., less than 30 ° C., It is less than 15 degreeC or less than 15 degreeC. In addition, after aging, tan δ greater than 0.05 can be maintained, which is not realized with materials known in the art to cure by hydrosilylation. See, for example, Comparative Example 4.

Claims (9)

An organosiloxane block copolymer,
Disiloxy unit of the formula _^[R 1 _{2 SiO 2/2]} of 40 to 80 mole percent,
Torishirokishi units of the formula ^[R _{2 SiO 3/2]} of 10-50 mole percent,
From 0.5 to 35 mole percent silanol groups [@SiOH];
Where:
Each R ¹ is independently a C ₁ -C ₃₀ hydrocarbyl or a C ₂ -C ₃₀ hydrocarbyl group containing at least one aliphatic unsaturated bond;
Each R ² is independently a C ₁ -C ₃₀ hydrocarbyl or a C ₂ -C ₃₀ hydrocarbyl group containing at least one aliphatic unsaturated bond;
here,
The disiloxy unit _^[R 1 _{2 SiO 2/2]} are arranged in linear blocks having 100 to 300 amino disiloxy unit on average per linear block _^[R 1 _{2 SiO 2/2]} ,
The trisiloxy units [R ² SiO _3/2 ] are arranged in a non-linear block having a molecular weight of at least 500 g / mol;
At least 30% of the non-linear blocks are cross-linked to each other;
Each linear block is linked to at least one non-linear block via a -Si-O-Si- bond;
The organosiloxane block copolymer has a weight average molecular weight of at least 20,000 g / mol, and
Said organosiloxane block copolymer comprises about 0.5 to about 4.5 mole percent of at least one _C 2 _{-C 30} hydrocarbyl group containing an aliphatic unsaturated bond,
Having an aliphatic unsaturated bond between two blocks of disiloxy units, between two blocks of trisiloxy units, or between blocks of disiloxy units and trisiloxy units;
Organosiloxane block copolymer. A composition,
A) A resin linear organosiloxane block copolymer,
Disiloxy unit of the formula _^[R 1 _{2 SiO 2/2]} of 40 to 80 mole percent,
Torishirokishi units of the formula ^[R _{2 SiO 3/2]} of 10-50 mole percent,
From 0.5 to 35 mole percent silanol groups [@SiOH];
Where:
Each R ¹ is independently C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation;
Each R ² is independently a C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation;
here,
The disiloxy unit _^[R 1 _{2 SiO 2/2]} are arranged in linear blocks having an average per linear block 50-300 amino disiloxy unit _^[R 1 _{2 SiO 2/2]} ,
The trisiloxy units [R ² SiO _3/2 ] are arranged in non-linear blocks having a molecular weight of at least 500 g / mol, at least 30% of the non-linear blocks being cross-linked to each other;
Each linear block is linked to at least one non-linear block, and
The organosiloxane block copolymer has a weight average molecular weight of at least 20,000 g / mol; a resin linear organosiloxane block copolymer;
B) a compound of formula ^R 1 ^R _{2 2} SiX,
Wherein each R ¹ is independently a C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation or a C ₂ -C ₃₀ hydrocarbyl group containing at least one aliphatic unsaturated bond;
Each R ² is independently a C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation or a C ₂ -C ₃₀ hydrocarbyl group containing at least one aliphatic unsaturated bond;
X ^is a -OR 4, F, Cl, Br , I, -OC (O) R 4, -N (R 4) 2, or a hydrolyzable group selected from -ON = ^CR _{4 2,} Wherein R ⁴ is hydrogen or an optionally substituted C ₁ -C ₆ alkyl group;
Containing the reaction product of
Said reaction product is an organosiloxane block copolymer, said organosiloxane block copolymer comprises a C ₂ -C ₃₀ hydrocarbyl group containing at least one aliphatic unsaturation of from about 0.5 to about 5 mole%, the composition object. A composition,
A) Formula:
There linear organosiloxanes having ^{_{R 1 3-p (E)}} p SiO (R 1 2 SiO 2/2) n Si (E) p R 1 3-p,
Wherein each R ¹ is independently C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation;
n is 50 to 300,
E ^{is, I, -OC (O) R} 4, -N (R 4) 2, or a hydrolyzable group selected from -ON = ^CR _{4 2,} wherein, ^{R 4} hydrogen or _{C 1} A C ₆ alkyl group; and
Each p is independently 1, 2 or 3, a linear organosiloxane;
B) Unit formula:
Containing ^{_{[R 1 2 R 2 SiO 1/2}} ] a [R 1 R 2 SiO 2/2] b [R 1 SiO 3/2] c [R 2 SiO 3/2] d [SiO 4/2] e An organosiloxane resin,
Where:
Each R ¹ is independently a C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation or a C ₂ -C ₃₀ hydrocarbyl group containing at least one aliphatic unsaturated bond;
Each R ² is independently a C ₁ -C ₃₀ hydrocarbyl group containing no aliphatic unsaturation or a C ₂ -C ₃₀ hydrocarbyl group containing at least one aliphatic unsaturated bond; ~ 35 mol% silanol groups [≡SiOH],
The subscripts a, b, c, d, and e represent the mole fraction of each siloxy unit present in the organosiloxane resin, and the range is
a is from about 0 to about 0.6;
b is from about 0 to about 0.6;
c is from about 0 to about 1,
d is about 0 to about 1,
e is from about 0 to about 0.6;
Wherein b + c + d + e> 0 and a reaction product with an organosiloxane resin satisfying 0.65 ≦ a + b + c + d + e ≦ 1,
Said reaction product is an organosiloxane block copolymer, said organosiloxane block copolymer comprises a C ₂ -C ₃₀ hydrocarbyl group containing at least one aliphatic unsaturation of from about 0.5 to about 5 mole%, the composition object. A composition,
A) Formula:
There linear organosiloxanes having ^{_{R 1 3-p (E)}} p SiO (R 1 2 SiO 2/2) n Si (E) p R 1 3-p,
Wherein each R ¹ is independently C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation;
n is 50 to 300,
E ^is a -OR 4, F, Cl, Br , I, -OC (O) R 4, -N (R 4) 2, or a hydrolyzable group selected from -ON = ^CR _{4 2,} Wherein R ⁴ is hydrogen or a C ₁ -C ₆ alkyl group;
Each p is independently 1, 2 or 3, a linear organosiloxane;
B) Unit formula:
Containing ^{_{[R 1 2 R 2 SiO 1/2}} ] a [R 1 R 2 SiO 2/2] b [R 1 SiO 3/2] c [R 2 SiO 3/2] d [SiO 4/2] e An organosiloxane resin,
Where:
Each R ¹ is independently C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation;
Each R ² is independently a C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation;
The organosiloxane resin contains 0 to 35 mol% of silanol groups [≡SiOH];
The subscripts a, b, c, d, and e represent the mole fraction of each siloxy unit present in the organosiloxane resin, and the range is
a is from about 0 to about 0.6;
b is from about 0 to about 0.6;
c is from about 0 to about 1,
d is about 0 to about 1,
e is from about 0 to about 0.6;
Wherein b + c + d + e> 0 and 0.65 ≦ a + b + c + d + e ≦ 1, and an organosiloxane resin;
C) a compound of the formula R ¹ _q SiX _4-q ,
Wherein each R ¹ is independently a C ₁ -C ₃₀ hydrocarbyl containing no aliphatic unsaturation or a C ₂ -C ₃₀ hydrocarbyl group containing at least one aliphatic unsaturated bond;
q is 0, 1, or 2,
Each X is ^{independently,} -OR 4, F, Cl, Br, I, -OC (O) R 4, -N (R 4) 2, or -ON = hydrolyzable selected from ^CR _{4 2} A compound, wherein R ⁴ is hydrogen or an optionally substituted C ₁ -C ₆ alkyl group,
Containing the reaction product of
Said reaction product is an organosiloxane block copolymer, said organosiloxane block copolymer comprises a C ₂ -C ₃₀ hydrocarbyl group containing at least one aliphatic unsaturation of from about 0.5 to about 5 mole%, the composition object. It said reaction product is contacted with a compound of the formula ^R ₅ q _{SiX 4-q,} wherein each ^{R 5} is _C 1 -C ₈ hydrocarbyl or _C 1 -C ₈ halogen substituted independently hydrocarbyl, each X is a ^independent -OR 4, F ^{and, Cl, Br, I, -OC} (O) R 4, -N (R 4) 2, or -ON = hydrolyzable group selected from ^CR _{4 2} Te, wherein, R ⁴ is substituted by hydrogen or is also good C ₁ -C ₆ alkyl group, a composition according to any one of claims 2-4.   The composition according to claim 3 or 4, wherein E is acetoxy and p is 1. Unit formula:
^{_{[R 1 2 R 2 SiO 1/2}} ] a [R 1 R 2 SiO 2/2] b [R 1 SiO 3/2] c [R 2 SiO 3/2] d have a _{[SiO 4/2] e} And
A compound containing 0 to 35 mol% of silanol groups [≡SiOH],
Where:
Each R ¹ independently represents H, a formula — [R ⁵ R ⁶ Si] _k [R ⁵ R ⁶ SiH] (wherein R ⁵ and R ⁶ independently represent H or aliphatic unsaturation, a _C 1 _{-C 30} hydrocarbyl free, k is _C 1 _{-C 30} hydrocarbyl containing no silane groups or aliphatic unsaturated and is) an integer of 0,
Each R ² is independently H or a group represented by the formula — [R ⁵ R ⁶ Si] _k [R ⁵ R ⁶ SiH] (where R ⁵ and R ⁶ are independently H or aliphatic unsaturated the a _C 1 _{-C 30} hydrocarbyl free, k is _C 1 _{-C 30} hydrocarbyl containing no silane groups of an a) integer of 0, the aliphatic unsaturation,
The subscripts a, b, c, d, and e represent the mole fraction of each siloxy unit present, and the range is:
a is from about 0 to about 0.6;
b is from about 0 to about 0.6;
c is from about 0 to about 1,
d is about 0 to about 1,
e is from about 0 to about 0.6;
However,
b + c + d + e> 0 and 0.65 ≦ a + b + c + d + e ≦ 1,
At least 1 mole percent of the R ¹ and / or R ² the compound is SiH containing H or silane group further comprises A composition according to any one of claims 2-6.   The composition according to any one of claims 2 to 7, further comprising a free resin that is not part of the block copolymer.   The composition according to any one of claims 2 to 4, wherein the composition is a solid.